Estolide Compositions Exhibiting Superior High-Performance Properties

ABSTRACT

Compounds and compositions, including engine oils and lubricant formulations comprising at least one estolide compound. Exemplary compositions comprise an estolide base oil and an additive package.

FIELD

The present disclosure relates to compositions containing one or moreestolide compounds and an additive package. In certain embodiments, thecomposition is a formulated engine oil.

BACKGROUND

Various types of petroleum-based lubricants suitable for use in engineshave been described. Such lubricants often contain a variety of additivecomponents in order for the lubricant to pass industry standard tests topermit use in engines. However, the use of such lubricants may result inthe dispersion of such lubricants into waterways, such as rivers, oceansand lakes. The petroleum base stock and additives of common enginelubricant formulations are typically non-biodegradable and can be toxic.Thus, the preparation and use of lubricants comprising biodegradablebase oils is desirable and has generated interest by both theenvironmental community and lubricant manufacturers.

SUMMARY

Described herein are compositions comprising at least one estolidecompound, and methods of making the same. In certain embodiments, thecomposition comprises a composition suitable for use as an enginelubricant. In certain embodiments, the composition comprises an estolidebase oil and an additive package. In certain embodiments, thecomposition comprises:

an additive package; and

at least one estolide compound selected from compounds of Formula I:

-   -   wherein    -   x is, independently for each occurrence, an integer selected        from 0 to 20;    -   y is, independently for each occurrence, an integer selected        from 0 to 20;    -   n is an integer equal to or greater than 0;    -   R₁ is an optionally substituted alkyl that is saturated or        unsaturated, and branched or unbranched; and    -   R₂ is selected from hydrogen and optionally substituted alkyl        that is saturated or unsaturated, and branched or unbranched;

wherein each fatty acid chain residue of said at least one estolidecompound is independently optionally substituted.

In certain embodiments, the composition comprises:

-   -   an additive package; and    -   at least one estolide compound selected from compounds of        Formula II:

-   -   wherein    -   m is an integer equal to or greater than 1;    -   n is an integer equal to or greater than 0;    -   R₁, independently for each occurrence, is an optionally        substituted alkyl that is saturated or unsaturated, and branched        or unbranched;    -   R₂ is selected from hydrogen and optionally substituted alkyl        that is saturated or unsaturated, and branched or unbranched;        and    -   R₃ and R₄, independently for each occurrence, are selected from        optionally substituted alkyl that is saturated or unsaturated,        and branched or unbranched.

DETAILED DESCRIPTION

The estolide compositions described herein may exhibit superioroxidative stability when compared to other lubricant and/orestolide-containing compositions. Exemplary compositions include, butare not limited to, coolants, fire-resistant and/or non-flammablefluids, dielectric fluids such as transformer fluids, greases, drillingfluids, crankcase oils, hydraulic fluids, passenger car motor oils(PCMO), two- and four-stroke lubricants, metalworking fluids, food-gradelubricants, refrigerating fluids, compressor fluids, and plasticizedcompositions.

The use of lubricants and lubricating fluid compositions may result inthe dispersion of such fluids, compounds, and/or compositions in theenvironment. Petroleum base oils used in common lubricant compositions,as well as additives, are typically non-biodegradable and can be toxic.The present disclosure provides for the preparation and use ofcompositions comprising partially or fully biodegradable base oils,including base oils comprising one or more estolides.

In certain embodiments, the lubricants and/or compositions comprisingone or more estolides are partially or fully biodegradable and therebypose diminished risk to the environment. In certain embodiments, thelubricants and/or compositions meet guidelines set for by theOrganization for Economic Cooperation and Development (OECD) fordegradation and accumulation testing. The OECD has indicated thatseveral tests may be used to determine the “ready biodegradability” oforganic chemicals. Aerobic ready biodegradability by OECD 301D measuresthe mineralization of the test sample to CO₂ in closed aerobicmicrocosms that simulate an aerobic aquatic environment, withmicroorganisms seeded from a waste-water treatment plant. OECD 301D isconsidered representative of most aerobic environments that are likelyto receive waste materials. Aerobic “ultimate biodegradability” can bedetermined by OECD 302D. Under OECD 302D, microorganisms arepre-acclimated to biodegradation of the test material during apre-incubation period, then incubated in sealed vessels with relativelyhigh concentrations of microorganisms and enriched mineral salts medium.OECD 302D ultimately determines whether the test materials arecompletely biodegradable, albeit under less stringent conditions than“ready biodegradability” assays.

As used in the present specification, the following words, phrases andsymbols are generally intended to have the meanings as set forth below,except to the extent that the context in which they are used indicatesotherwise. The following abbreviations and terms have the indicatedmeanings throughout:

A dash (“—”) that is not between two letters or symbols is used toindicate a point of attachment for a substituent. For example, —C(O)NH₂is attached through the carbon atom.

“Alkoxy” by itself or as part of another substituent refers to a radical—OR³¹ where R³¹ is alkyl, cycloalkyl, cycloalkylalkyl, aryl, orarylalkyl, which can be substituted, as defined herein. In someembodiments, alkoxy groups have from 1 to 8 carbon atoms. In someembodiments, alkoxy groups have 1, 2, 3, 4, 5, 6, 7, or 8 carbon atoms.Examples of alkoxy groups include, but are not limited to, methoxy,ethoxy, propoxy, butoxy, cyclohexyloxy, and the like.

“Alkyl” by itself or as part of another substituent refers to asaturated or unsaturated, branched, or straight-chain monovalenthydrocarbon radical derived by the removal of one hydrogen atom from asingle carbon atom of a parent alkane, alkene, or alkyne. Examples ofalkyl groups include, but are not limited to, methyl; ethyls such asethanyl, ethenyl, and ethynyl; propyls such as propan-1-yl, propan-2-yl,prop-1-en-1-yl, prop-1-en-2-yl, prop-2-en-1-yl (allyl), prop-1-yn-1-yl,prop-2-yn-1-yl, etc.; butyls such as butan-1-yl, butan-2-yl,2-methyl-propan-1-yl, 2-methyl-propan-2-yl, but-1-en-1-yl,but-1-en-2-yl, 2-methyl-prop-1-en-1-yl, but-2-en-1-yl, but-2-en-2-yl,buta-1,3-dien-1-yl, buta-1,3-dien-2-yl, but-1-yn-1-yl, but-1-yn-3-yl,but-3-yn-1-yl, etc.; and the like.

Unless otherwise indicated, the term “alkyl” is specifically intended toinclude groups having any degree or level of saturation, i.e., groupshaving exclusively single carbon-carbon bonds, groups having one or moredouble carbon-carbon bonds, groups having one or more triplecarbon-carbon bonds, and groups having mixtures of single, double, andtriple carbon-carbon bonds. Where a specific level of saturation isintended, the terms “alkanyl,” “alkenyl,” and “alkynyl” are used. Incertain embodiments, an alkyl group comprises from 1 to 40 carbon atoms,in certain embodiments, from 1 to 22 or 1 to 18 carbon atoms, in certainembodiments, from 1 to 16 or 1 to 8 carbon atoms, and in certainembodiments from 1 to 6 or 1 to 3 carbon atoms. In certain embodiments,an alkyl group comprises from 8 to 22 carbon atoms, in certainembodiments, from 8 to 18 or 8 to 16. In some embodiments, the alkylgroup comprises from 3 to 20 or 7 to 17 carbons. In some embodiments,the alkyl group comprises 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14,15, 16, 17, 18, 19, 20, 21, or 22 carbon atoms.

“Aryl” by itself or as part of another substituent refers to amonovalent aromatic hydrocarbon radical derived by the removal of onehydrogen atom from a single carbon atom of a parent aromatic ringsystem. Aryl encompasses 5- and 6-membered carbocyclic aromatic rings,for example, benzene; bicyclic ring systems wherein at least one ring iscarbocyclic and aromatic, for example, naphthalene, indane, andtetralin; and tricyclic ring systems wherein at least one ring iscarbocyclic and aromatic, for example, fluorene. Aryl encompassesmultiple ring systems having at least one carbocyclic aromatic ringfused to at least one carbocyclic aromatic ring, cycloalkyl ring, orheterocycloalkyl ring. For example, aryl includes 5- and 6-memberedcarbocyclic aromatic rings fused to a 5- to 7-membered non-aromaticheterocycloalkyl ring containing one or more heteroatoms chosen from N,O, and S. For such fused, bicyclic ring systems wherein only one of therings is a carbocyclic aromatic ring, the point of attachment may be atthe carbocyclic aromatic ring or the heterocycloalkyl ring. Examples ofaryl groups include, but are not limited to, groups derived fromaceanthrylene, acenaphthylene, acephenanthrylene, anthracene, azulene,benzene, chrysene, coronene, fluoranthene, fluorene, hexacene,hexaphene, hexalene, as-indacene, s-indacene, indane, indene,naphthalene, octacene, octaphene, octalene, ovalene, penta-2,4-diene,pentacene, pentalene, pentaphene, perylene, phenalene, phenanthrene,picene, pleiadene, pyrene, pyranthrene, rubicene, triphenylene,trinaphthalene, and the like. In certain embodiments, an aryl group cancomprise from 5 to 20 carbon atoms, and in certain embodiments, from 5to 12 carbon atoms. In certain embodiments, an aryl group can comprise5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbonatoms. Aryl, however, does not encompass or overlap in any way withheteroaryl, separately defined herein. Hence, a multiple ring system inwhich one or more carbocyclic aromatic rings is fused to aheterocycloalkyl aromatic ring, is heteroaryl, not aryl, as definedherein.

“Arylalkyl” by itself or as part of another substituent refers to anacyclic alkyl radical in which one of the hydrogen atoms bonded to acarbon atom, typically a terminal or sp³ carbon atom, is replaced withan aryl group. Examples of arylalkyl groups include, but are not limitedto, benzyl, 2-phenylethan-1-yl, 2-phenylethen-1-yl, naphthylmethyl,2-naphthylethan-1-yl, 2-naphthylethen-1-yl, naphthobenzyl,2-naphthophenylethan-1-yl, and the like. Where specific alkyl moietiesare intended, the nomenclature arylalkanyl, arylalkenyl, or arylalkynylis used. In certain embodiments, an arylalkyl group is C₇₋₃₀ arylalkyl,e.g., the alkanyl, alkenyl, or alkynyl moiety of the arylalkyl group isC₁₋₁₀ and the aryl moiety is C₆₋₂₀, and in certain embodiments, anarylalkyl group is C₇₋₂₀ arylalkyl, e.g., the alkanyl, alkenyl, oralkynyl moiety of the arylalkyl group is C₁₋₈ and the aryl moiety isC₆₋₁₂.

Estolide “base oil” and “base stock”, unless otherwise indicated, referto any composition comprising one or more estolide compounds. It shouldbe understood that an estolide “base oil” or “base stock” is not limitedto compositions for a particular use, and may generally refer tocompositions comprising one or more estolides, including mixtures ofestolides. Estolide base oils and base stocks can also include compoundsother than estolides.

“Antioxidant” refers to a substance that is capable of inhibiting,preventing, reducing, or ameliorating oxidative reactions in anothersubstance (e.g., base oil such as an estolide compound) when theantioxidant is used in a composition (e.g., lubricant formulation) thatincludes such other substances. An example of an “antioxidant” is anoxygen scavenger.

“Compounds” refers to compounds encompassed by structural Formula I andII herein and includes any specific compounds within the formula whosestructure is disclosed herein. Compounds may be identified either bytheir chemical structure and/or chemical name. When the chemicalstructure and chemical name conflict, the chemical structure isdeterminative of the identity of the compound. The compounds describedherein may contain one or more chiral centers and/or double bonds andtherefore may exist as stereoisomers such as double-bond isomers (i.e.,geometric isomers), enantiomers, or diastereomers. Accordingly, anychemical structures within the scope of the specification depicted, inwhole or in part, with a relative configuration encompass all possibleenantiomers and stereoisomers of the illustrated compounds including thestereoisomerically pure form (e.g., geometrically pure, enantiomericallypure, or diastereomerically pure) and enantiomeric and stereoisomericmixtures. Enantiomeric and stereoisomeric mixtures may be resolved intotheir component enantiomers or stereoisomers using separation techniquesor chiral synthesis techniques well known to the skilled artisan.

For the purposes of the present disclosure, “chiral compounds” arecompounds having at least one center of chirality (i.e. at least oneasymmetric atom, in particular at least one asymmetric C atom), havingan axis of chirality, a plane of chirality or a screw structure.“Achiral compounds” are compounds which are not chiral.

Compounds of Formula I and II include, but are not limited to, opticalisomers of compounds of Formula I and II, racemates thereof, and othermixtures thereof. In such embodiments, the single enantiomers ordiastereomer I and II s, i.e., optically active forms, can be obtainedby asymmetric synthesis or by resolution of the racemates. Resolution ofthe racemates may be accomplished by, for example, chromatography,using, for example a chiral high-pressure liquid chromatography (HPLC)column. However, unless otherwise stated, it should be assumed thatFormula I and II cover all asymmetric variants of the compoundsdescribed herein, including isomers, racemates, enantiomers,diastereomers, and other mixtures thereof. In addition, compounds ofFormula I and II include Z- and E-forms (e.g., cis- and trans-forms) ofcompounds with double bonds. The compounds of Formula I and II may alsoexist in several tautomeric forms including the enol form, the ketoform, and mixtures thereof. Accordingly, the chemical structuresdepicted herein encompass all possible tautomeric forms of theillustrated compounds.

“Cycloalkyl” by itself or as part of another substituent refers to asaturated or unsaturated cyclic alkyl radical. Where a specific level ofsaturation is intended, the nomenclature “cycloalkanyl” or“cycloalkenyl” is used. Examples of cycloalkyl groups include, but arenot limited to, groups derived from cyclopropane, cyclobutane,cyclopentane, cyclohexane, and the like. In certain embodiments, acycloalkyl group is C₃₋₁₅ cycloalkyl, and in certain embodiments, C₃₋₁₂cycloalkyl or C₅₋₁₂ cycloalkyl. In certain embodiments, a cycloalkylgroup is a C₅, C₆, C₇, C₈, C₉, C₁₀, C₁₁, C₁₂, C₁₃, C₁₄, or C₁₅cycloalkyl.

“Cycloalkylalkyl” by itself or as part of another substituent refers toan acyclic alkyl radical in which one of the hydrogen atoms bonded to acarbon atom, typically a terminal or sp³ carbon atom, is replaced with acycloalkyl group. Where specific alkyl moieties are intended, thenomenclature cycloalkylalkanyl, cycloalkylalkenyl, or cycloalkylalkynylis used. In certain embodiments, a cycloalkylalkyl group is C₇₋₃₀cycloalkylalkyl, e.g., the alkanyl, alkenyl, or alkynyl moiety of thecycloalkylalkyl group is C₁₋₁₀ and the cycloalkyl moiety is C₆₋₂₀, andin certain embodiments, a cycloalkylalkyl group is C₇₋₂₀cycloalkylalkyl, e.g., the alkanyl, alkenyl, or alkynyl moiety of thecycloalkylalkyl group is C₁₋₈ and the cycloalkyl moiety is C₄₋₂₀ orC₆₋₁₂.

“Halogen” refers to a fluoro, chloro, bromo, or iodo group.

“Heteroaryl” by itself or as part of another substituent refers to amonovalent heteroaromatic radical derived by the removal of one hydrogenatom from a single atom of a parent heteroaromatic ring system.Heteroaryl encompasses multiple ring systems having at least onearomatic ring fused to at least one other ring, which can be aromatic ornon-aromatic in which at least one ring atom is a heteroatom. Heteroarylencompasses 5- to 12-membered aromatic, such as 5- to 7-membered,monocyclic rings containing one or more, for example, from 1 to 4, or incertain embodiments, from 1 to 3, heteroatoms chosen from N, O, and S,with the remaining ring atoms being carbon; and bicyclicheterocycloalkyl rings containing one or more, for example, from 1 to 4,or in certain embodiments, from 1 to 3, heteroatoms chosen from N, O,and S, with the remaining ring atoms being carbon and wherein at leastone heteroatom is present in an aromatic ring. For example, heteroarylincludes a 5- to 7-membered heterocycloalkyl, aromatic ring fused to a5- to 7-membered cycloalkyl ring. For such fused, bicyclic heteroarylring systems wherein only one of the rings contains one or moreheteroatoms, the point of attachment may be at the heteroaromatic ringor the cycloalkyl ring. In certain embodiments, when the total number ofN, S, and O atoms in the heteroaryl group exceeds one, the heteroatomsare not adjacent to one another. In certain embodiments, the totalnumber of N, S, and O atoms in the heteroaryl group is not more thantwo. In certain embodiments, the total number of N, S, and O atoms inthe aromatic heterocycle is not more than one. Heteroaryl does notencompass or overlap with aryl as defined herein.

Examples of heteroaryl groups include, but are not limited to, groupsderived from acridine, arsindole, carbazole, β-carboline, chromane,chromene, cinnoline, furan, imidazole, indazole, indole, indoline,indolizine, isobenzofuran, isochromene, isoindole, isoindoline,isoquinoline, isothiazole, isoxazole, naphthyridine, oxadiazole,oxazole, perimidine, phenanthridine, phenanthroline, phenazine,phthalazine, pteridine, purine, pyran, pyrazine, pyrazole, pyridazine,pyridine, pyrimidine, pyrrole, pyrrolizine, quinazoline, quinoline,quinolizine, quinoxaline, tetrazole, thiadiazole, thiazole, thiophene,triazole, xanthene, and the like. In certain embodiments, a heteroarylgroup is from 5- to 20-membered heteroaryl, and in certain embodimentsfrom 5- to 12-membered heteroaryl or from 5- to 10-membered heteroaryl.In certain embodiments, a heteroaryl group is a 5-, 6-, 7-, 8-, 9-, 10-,11-, 12-, 13-, 14-, 15-, 16-, 17-, 18-, 19-, or 20-membered heteroaryl.In certain embodiments heteroaryl groups are those derived fromthiophene, pyrrole, benzothiophene, benzofuran, indole, pyridine,quinoline, imidazole, oxazole, and pyrazine.

“Heteroarylalkyl” by itself or as part of another substituent refers toan acyclic alkyl radical in which one of the hydrogen atoms bonded to acarbon atom, typically a terminal or sp³ carbon atom, is replaced with aheteroaryl group. Where specific alkyl moieties are intended, thenomenclature heteroarylalkanyl, heteroarylalkenyl, or heteroarylalkynylis used. In certain embodiments, a heteroarylalkyl group is a 6- to30-membered heteroarylalkyl, e.g., the alkanyl, alkenyl, or alkynylmoiety of the heteroarylalkyl is 1- to 10-membered and the heteroarylmoiety is a 5- to 20-membered heteroaryl, and in certain embodiments, 6-to 20-membered heteroarylalkyl, e.g., the alkanyl, alkenyl, or alkynylmoiety of the heteroarylalkyl is 1- to 8-membered and the heteroarylmoiety is a 5- to 12-membered heteroaryl.

“Heterocycloalkyl” by itself or as part of another substituent refers toa partially saturated or unsaturated cyclic alkyl radical in which oneor more carbon atoms (and any associated hydrogen atoms) areindependently replaced with the same or different heteroatom. Examplesof heteroatoms to replace the carbon atom(s) include, but are notlimited to, N, P, O, S, Si, etc. Where a specific level of saturation isintended, the nomenclature “heterocycloalkanyl” or “heterocycloalkenyl”is used. Examples of heterocycloalkyl groups include, but are notlimited to, groups derived from epoxides, azirines, thiiranes,imidazolidine, morpholine, piperazine, piperidine, pyrazolidine,pyrrolidine, quinuclidine, and the like.

“Heterocycloalkylalkyl” by itself or as part of another substituentrefers to an acyclic alkyl radical in which one of the hydrogen atomsbonded to a carbon atom, typically a terminal or sp³ carbon atom, isreplaced with a heterocycloalkyl group. Where specific alkyl moietiesare intended, the nomenclature heterocycloalkylalkanyl,heterocycloalkylalkenyl, or heterocycloalkylalkynyl is used. In certainembodiments, a heterocycloalkylalkyl group is a 6- to 30-memberedheterocycloalkylalkyl, e.g., the alkanyl, alkenyl, or alkynyl moiety ofthe heterocycloalkylalkyl is 1- to 10-membered and the heterocycloalkylmoiety is a 5- to 20-membered heterocycloalkyl, and in certainembodiments, 6- to 20-membered heterocycloalkylalkyl, e.g., the alkanyl,alkenyl, or alkynyl moiety of the heterocycloalkylalkyl is 1- to8-membered and the heterocycloalkyl moiety is a 5- to 12-memberedheterocycloalkyl.

“Mixture” refers to a collection of molecules or chemical substances.Each component in a mixture can be independently varied. A mixture maycontain, or consist essentially of, two or more substances intermingledwith or without a constant percentage composition, wherein eachcomponent may or may not retain its essential original properties, andwhere molecular phase mixing may or may not occur. In mixtures, thecomponents making up the mixture may or may not remain distinguishablefrom each other by virtue of their chemical structure.

“Parent aromatic ring system” refers to an unsaturated cyclic orpolycyclic ring system having a conjugated π (pi) electron system.Included within the definition of “parent aromatic ring system” arefused ring systems in which one or more of the rings are aromatic andone or more of the rings are saturated or unsaturated, such as, forexample, fluorene, indane, indene, phenalene, etc. Examples of parentaromatic ring systems include, but are not limited to, aceanthrylene,acenaphthylene, acephenanthrylene, anthracene, azulene, benzene,chrysene, coronene, fluoranthene, fluorene, hexacene, hexaphene,hexalene, as-indacene, s-indacene, indane, indene, naphthalene,octacene, octaphene, octalene, ovalene, penta-2,4-diene, pentacene,pentalene, pentaphene, perylene, phenalene, phenanthrene, picene,pleiadene, pyrene, pyranthrene, rubicene, triphenylene, trinaphthalene,and the like.

“Parent heteroaromatic ring system” refers to a parent aromatic ringsystem in which one or more carbon atoms (and any associated hydrogenatoms) are independently replaced with the same or different heteroatom.Examples of heteroatoms to replace the carbon atoms include, but are notlimited to, N, P, O, S, Si, etc. Specifically included within thedefinition of “parent heteroaromatic ring systems” are fused ringsystems in which one or more of the rings are aromatic and one or moreof the rings are saturated or unsaturated, such as, for example,arsindole, benzodioxan, benzofuran, chromane, chromene, indole,indoline, xanthene, etc. Examples of parent heteroaromatic ring systemsinclude, but are not limited to, arsindole, carbazole, β-carboline,chromane, chromene, cinnoline, furan, imidazole, indazole, indole,indoline, indolizine, isobenzofuran, isochromene, isoindole,isoindoline, isoquinoline, isothiazole, isoxazole, naphthyridine,oxadiazole, oxazole, perimidine, phenanthridine, phenanthroline,phenazine, phthalazine, pteridine, purine, pyran, pyrazine, pyrazole,pyridazine, pyridine, pyrimidine, pyrrole, pyrrolizine, quinazoline,quinoline, quinolizine, quinoxaline, tetrazole, thiadiazole, thiazole,thiophene, triazole, xanthene, and the like.

“Substituted” refers to a group in which one or more hydrogen atoms areindependently replaced with the same or different substituent(s).Examples of substituents include, but are not limited to, —R⁶⁴, —R⁶⁰,—O⁻, —OH, ═O, —OR⁶⁰, —SR⁶⁰, —S⁻, ═S, —NR⁶⁰R⁶¹, ═NR⁶⁰, —CN, —CF₃, —OCN,—SCN, —NO, —NO₂, ═N₂, —N₃, —S(O)₂O⁻, —S(O)₂OH, —S(O)₂R⁶⁰, —OS(O₂)O⁻,—OS(O)₂R⁶⁰, —P(O)(O⁻)₂, —P(O)(OR⁶⁰)(O⁻), —OP(O)(OR⁶⁰)(OR⁶¹), —C(O)R⁶⁰,—C(S)R⁶⁰, —C(O)OR⁶⁰, —C(O)NR⁶⁰R⁶¹, —C(O)O⁻, —C(S)OR⁶⁰, —NR⁶²C(O)NR⁶⁰R⁶¹,—NR⁶²C(S)NR⁶⁰R⁶¹, —NR⁶²C(NR⁶³)NR⁶⁰R⁶¹, —C(NR⁶²)NR⁶⁰R⁶¹, —S(O)₂, NR⁶⁰R⁶¹,—NR⁶³S(O)₂R⁶⁰, —NR⁶³C(O)R⁶⁰, and —S(O)R⁶⁰;

wherein each —R⁶⁴ is independently a halogen; each R⁶⁰ and R⁶¹ areindependently alkyl, substituted alkyl, alkoxy, substituted alkoxy,cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substitutedheterocycloalkyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, arylalkyl, substituted arylalkyl, heteroarylalkyl, orsubstituted heteroarylalkyl, or R⁶⁰ and R⁶¹ together with the nitrogenatom to which they are bonded form a heterocycloalkyl, substitutedheterocycloalkyl, heteroaryl, or substituted heteroaryl ring, and R⁶²and R⁶³ are independently alkyl, substituted alkyl, aryl, substitutedaryl, arylalkyl, substituted arylalkyl, cycloalkyl, substitutedcycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, heteroaryl,substituted heteroaryl, heteroarylalkyl, or substituted heteroarylalkyl,or R⁶² and R⁶³ together with the atom to which they are bonded form oneor more heterocycloalkyl, substituted heterocycloalkyl, heteroaryl, orsubstituted heteroaryl rings;

wherein the “substituted” substituents, as defined above for R⁶⁰, R⁶¹,R⁶², and R⁶³, are substituted with one or more, such as one, two, orthree, groups independently selected from alkyl, -alkylOH, O-haloalkyl,alkylNH₂, alkoxy, cycloalkyl, cycloalkylalkyl, heterocycloalkyl,heterocycloalkylalkyl, aryl, heteroaryl, arylalkyl, heteroarylalkyl,—O⁻, —OH, ═O, —O-alkyl, —O-aryl, —O-heteroarylalkyl, —O-cycloalkyl,—O-heterocycloalkyl, —SH, —S⁻, ═S, —S-alkyl, —S-aryl,—S-heteroarylalkyl, —S-cycloalkyl, —S-heterocycloalkyl, —NH₂, ═NH, —CN,—CF₃, —OCN, —SCN, —NO, —NO₂, ═N₂, —N₃, —S(O)₂O⁻, —S(O)₂, —S(O)₂OH,—OS(O₂)O⁻, —SO₂(alkyl), —SO₂(phenyl), —SO₂(haloalkyl), —SO₂NH₂,SO₂NH(alkyl), SO₂NH(phenyl), —P(O)(O⁻)₂, —P(O)(O-alkyl)(O⁻),—OP(O)(O-alkyl)(O-alkyl), CO₂H, C(O)O(alkyl), CON(alkyl)(alkyl),—CONH(alkyl), CONH₂, C(O)(alkyl), C(O)(phenyl), C(O)(haloalkyl),OC(O)(alkyl), N(alkyl)(alkyl), NH(alkyl), N(alkyl)(alkylphenyl),NH(alkylphenyl), NHC(O)(alkyl), NHC(O)(phenyl), —N(alkyl)C(O)(alkyl),and N(alkyl)C(O)(phenyl).

As used in this specification and the appended claims, the articles “a,”“an,” and “the” include plural referents unless expressly andunequivocally limited to one referent.

All numerical ranges herein include all numerical values and ranges ofall numerical values within the recited range of numerical values.

The present disclosure relates compositions comprising one or moreestolide compounds, and methods of making the same. In certainembodiments, the composition comprises a composition suitable for use asan engine lubricant. In certain embodiments, the composition comprisesan estolide base oil and an additive package. In certain embodiments,the composition comprises:

-   -   an additive package; and    -   at least one estolide compound selected from compounds of        Formula I:

-   -   wherein    -   x is, independently for each occurrence, an integer selected        from 0 to 20;    -   y is, independently for each occurrence, an integer selected        from 0 to 20;    -   n is an integer equal to or greater than 0;    -   R₁ is an optionally substituted alkyl that is saturated or        unsaturated, and branched or unbranched; and    -   R₂ is selected from hydrogen and optionally substituted alkyl        that is saturated or unsaturated, and branched or unbranched;    -   wherein each fatty acid chain residue of said at least one        estolide compound is independently optionally substituted.

In certain embodiments, the composition comprises:

-   -   an additive package; and    -   at least one estolide compound selected from compounds of        Formula II:

-   -   wherein    -   m is an integer equal to or greater than 1;    -   n is an integer equal to or greater than 0;    -   R₁, independently for each occurrence, is an optionally        substituted alkyl that is saturated or unsaturated, and branched        or unbranched;    -   R₂ is selected from hydrogen and optionally substituted alkyl        that is saturated or unsaturated, and branched or unbranched;        and    -   R₃ and R₄, independently for each occurrence, are selected from        optionally substituted alkyl that is saturated or unsaturated,        and branched or unbranched.

In certain embodiments, the composition comprises at least one estolidecompound of Formula I or II, wherein R₁ is hydrogen.

The terms “chain” or “fatty acid chain” or “fatty acid chain residue,”as used with respect to the estolide compounds of Formula I and II,refer to one or more of the fatty acid residues incorporated in estolidecompounds, e.g., R₃ or R₄ of Formula II, or the structures representedby CH₃(CH₂)_(y)CH(CH₂)_(x)C(O)O— in Formula I.

The R₁ in Formula I and II at the top of each Formula shown is anexample of what may be referred to as a “cap” or “capping material,” asit “caps” the top of the estolide. Similarly, the capping group may bean organic acid residue of general formula —OC(O)-alkyl, i.e., acarboxylic acid with a substituted or unsubstituted, saturated orunsaturated, and/or branched or unbranched alkyl as defined herein, or aformic acid residue. In certain embodiments, the “cap” or “cappinggroup” is a fatty acid. In certain embodiments, the capping group,regardless of size, is substituted or unsubstituted, saturated orunsaturated, and/or branched or unbranched. The cap or capping materialmay also be referred to as the primary or alpha (α) chain.

Depending on the manner in which the estolide is synthesized, the cap orcapping group alkyl may be the only alkyl from an organic acid residuein the resulting estolide that is unsaturated. In certain embodiments,it may be desirable to use a saturated organic or fatty-acid cap toincrease the overall saturation of the estolide and/or to increase theresulting estolide's stability. For example, in certain embodiments, itmay be desirable to provide a method of providing a saturated cappedestolide by hydrogenating an unsaturated cap using any suitable methodsavailable to those of ordinary skill in the art. Hydrogenation may beused with various sources of the fatty-acid feedstock, which may includemono- and/or polyunsaturated fatty acids. Without being bound to anyparticular theory, in certain embodiments, hydrogenating the estolidemay help to improve the overall stability of the molecule. However, afully-hydrogenated estolide, such as an estolide with a larger fattyacid cap, may exhibit increased pour point temperatures. In certainembodiments, it may be desirable to offset any loss in desirablepour-point characteristics by using shorter, saturated cappingmaterials.

The R₄C(O)O— of Formula II or structure CH₃(CH₂)_(y)CH(CH₂)_(x)C(O)O— ofFormula I serve as the “base” or “base chain residue” of the estolide.Depending on the manner in which the estolide is synthesized, the baseorganic acid or fatty acid residue may be the only residue that remainsin its free-acid form after the initial synthesis of the estolide.However, in certain embodiments, in an effort to alter or improve theproperties of the estolide, the free acid may be reacted with any numberof substituents. For example, it may be desirable to react the free acidestolide with alcohols, glycols, amines, or other suitable reactants toprovide the corresponding ester, amide, or other reaction products. Thebase or base chain residue may also be referred to as tertiary or gamma(γ) chains.

The R₃C(O)O— of Formula II or structure CH₃(CH₂)_(y)CH(CH₂)_(x)C(O)O— ofFormula I are linking residues that link the capping material and thebase fatty-acid residue together. There may be any number of linkingresidues in the estolide, including when n=0 and the estolide is in itsdimer form. Depending on the manner in which the estolide is prepared, alinking residue may be a fatty acid and may initially be in anunsaturated form during synthesis. In some embodiments, the estolidewill be formed when a catalyst is used to produce a carbocation at thefatty acid's site of unsaturation, which is followed by nucleophilicattack on the carbocation by the carboxylic group of another fatty acid.In some embodiments, it may be desirable to have a linking fatty acidthat is monounsaturated so that when the fatty acids link together, allof the sites of unsaturation are eliminated. The linking residue(s) mayalso be referred to as secondary or beta (β) chains.

In certain embodiments, the cap is an acetyl group, the linkingresidue(s) is one or more fatty acid residues, and the base chainresidue is a fatty acid residue. In certain embodiments, the linkingresidues present in an estolide differ from one another. In certainembodiments, one or more of the linking residues differs from the basechain residue.

As noted above, in certain embodiments, suitable unsaturated fatty acidsfor preparing the estolides may include any mono- or polyunsaturatedfatty acid. For example, monounsaturated fatty acids, along with asuitable catalyst, will form a single carbocation that allows for theaddition of a second fatty acid, whereby a single link between two fattyacids is formed. Suitable monounsaturated fatty acids may include, butare not limited to, palmitoleic acid (16:1), vaccenic acid (18:1), oleicacid (18:1), eicosenoic acid (20:1), erucic acid (22:1), and nervonicacid (24:1). In addition, in certain embodiments, polyunsaturated fattyacids may be used to create estolides. Suitable polyunsaturated fattyacids may include, but are not limited to, hexadecatrienoic acid (16:3),alpha-linolenic acid (18:3), stearidonic acid (18:4), eicosatrienoicacid (20:3), eicosatetraenoic acid (20:4), eicosapentaenoic acid (20:5),heneicosapentaenoic acid (21:5), docosapentaenoic acid (22:5),docosahexaenoic acid (22:6), tetracosapentaenoic acid (24:5),tetracosahexaenoic acid (24:6), linoleic acid (18:2), gamma-linoleicacid (18:3), eicosadienoic acid (20:2), dihomo-gamma-linolenic acid(20:3), arachidonic acid (20:4), docosadienoic acid (20:2), adrenic acid(22:4), docosapentaenoic acid (22:5), tetracosatetraenoic acid (22:4),tetracosapentaenoic acid (24:5), pinolenic acid (18:3), podocarpic acid(20:3), rumenic acid (18:2), alpha-calendic acid (18:3), beta-calendicacid (18:3), jacaric acid (18:3), alpha-eleostearic acid (18:3),beta-eleostearic (18:3), catalpic acid (18:3), punicic acid (18:3),rumelenic acid (18:3), alpha-parinaric acid (18:4), beta-parinaric acid(18:4), and bosseopentaenoic acid (20:5). Other exemplary fatty acidsmay include terminally-unsaturated fatty acids such as 10-undecenoicacid, which may be derived from castor oil. In certain embodiments,hydroxy fatty acids may be polymerized or homopolymerized by reactingthe carboxylic acid functionality of one fatty acid with the hydroxyfunctionality of a second fatty acid. Exemplary hydroxyl fatty acidsinclude, but are not limited to, ricinoleic acid, 6-hydroxystearic acid,9,10-dihydroxystearic acid, 12-hydroxystearic acid, and14-hydroxystearic acid.

The process for preparing the estolide compounds described herein mayinclude the use of any natural or synthetic fatty acid source. However,it may be desirable to source the fatty acids from a renewablebiological feedstock. For example, suitable starting materials ofbiological origin include, but are not limited to, plant fats, plantoils, plant waxes, animal fats, animal oils, animal waxes, fish fats,fish oils, fish waxes, algal oils and mixtures of two or more thereof.Other potential fatty acid sources include, but are not limited to,waste and recycled food-grade fats and oils, fats, oils, and waxesobtained by genetic engineering, fossil fuel-based materials and othersources of the materials desired.

In certain embodiments, the estolide compounds described herein may beprepared from non-naturally occurring fatty acids derived from naturallyoccurring feedstocks. In certain embodiments, the estolides are preparedfrom synthetic fatty acid reactants derived from naturally occurringfeedstocks such as vegetable oils. For example, the synthetic fatty acidreactants may be prepared by cleaving fragments from larger fatty acidresidues occurring in natural oils such as triglycerides using, forexample, a cross-metathesis catalyst and alpha-olefin(s). The resultingtruncated fatty acid residue(s) may be liberated from the glycerinebackbone using any suitable hydrolytic and/or transesterificationprocesses known to those of skill in the art. An exemplary fatty acidreactants include 9-dodecenoic acid and 9-decenoic acid, which may beprepared via the cross metathesis of an oleic acid residue with1-butene.

In some embodiments, the compound comprises chain residues of varyinglengths. In some embodiments, x is, independently for each occurrence,an integer selected from 0 to 20, 0 to 18, 0 to 16, 0 to 14, 1 to 12, 1to 10, 2 to 8, 6 to 8, or 4 to 6. In some embodiments, x is,independently for each occurrence, an integer selected from 7 and 8. Insome embodiments, x is, independently for each occurrence, an integerselected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16,17, 18, 19, and 20. In certain embodiments, for at least one chainresidue, x is an integer selected from 7 and 8.

In some embodiments, y is, independently for each occurrence, an integerselected from 0 to 20, 0 to 18, 0 to 16, 0 to 14, 1 to 12, 1 to 10, 2 to8, 6 to 8, or 4 to 6. In some embodiments, y is, independently for eachoccurrence, an integer selected from 7 and 8. In some embodiments, y is,independently for each occurrence, an integer selected from 0, 1, 2, 3,4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20. Incertain embodiments, for at least one chain residue, y is an integerselected from 7 and 8. In some embodiments, for at least one chainresidue, y is an integer selected from 0 to 6, or 1 and 2. In certainembodiments, y is, independently for each occurrence, an integerselected from 1 to 6, or 1 and 2. In certain embodiments, y is 0.

In some embodiments, x+y is, independently for each chain, an integerselected from 0 to 40, 0 to 20, 10 to 20, or 12 to 18. In someembodiments, x+y is, independently for each chain, an integer selectedfrom 13 to 15. In some embodiments, x+y is 15. In some embodiments, x+yis, independently for each chain, an integer selected from 6, 7, 8, 9,10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, and 24.

In some embodiments, the estolide compound of Formula I or II maycomprise any number of fatty acid residues to form an “n-mer” estolide.For example, the estolide may be in its dimer (n=0), trimer (n=1),tetramer (n=2), pentamer (n=3), hexamer (n=4), heptamer (n=5), octamer(n=6), nonamer (n=7), or decamer (n=8) form. In some embodiments, n isan integer selected from 0 to 20, 0 to 18, 0 to 16, 0 to 14, 0 to 12, 0to 10, 0 to 8, or 0 to 6. In some embodiments, n is an integer selectedfrom 0 to 4. In some embodiments, n is 0 or greater than 0. In someembodiments, n is 1, wherein said at least one compound of Formula I orII comprises the trimer. In some embodiments, n is greater than 1. Insome embodiments, n is an integer selected from 0, 1, 2, 3, 4, 5, 6, 7,8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20.

In some embodiments, R₁ of Formula I or II is an optionally substitutedalkyl that is saturated or unsaturated, and branched or unbranched. Insome embodiments, the alkyl group is a C₁ to C₄₀ alkyl, C₁ to C₂₂ alkylor C₁ to C₁₈ alkyl. In some embodiments, the alkyl group is selectedfrom C₇ to C₁₇ alkyl. In some embodiments, R₁ is selected from C₇ alkyl,C₉ alkyl, C₁₁ alkyl, C₁₃ alkyl, C₁₅ alkyl, and C₁₇ alkyl. In someembodiments, R₁ is selected from C₁₃ to C₁₇ alkyl, such as from C₁₃alkyl, C₁₅ alkyl, and C₁₇ alkyl. In some embodiments, R₁ is a C₁, C₂,C₃, C₄, C₅, C₆, C₇, C₈, C₉, C₁₀, C₁₁, C₁₂, C₁₃, C₁₄, C₁₅, C₁₆, C₁₇, C₁₈,C₁₉, C₂₀, C₂₁, or C₂₂ alkyl. In certain embodiments, R₁ is saturated. Incertain embodiments, R₁ is unbranched.

In some embodiments, R₂ of Formula I or II is an optionally substitutedalkyl that is saturated or unsaturated, and branched or unbranched. Insome embodiments, the alkyl group is a C₁ to C₄₀ alkyl, C₁ to C₂₂ alkylor C₁ to C₁₈ alkyl. In some embodiments, the alkyl group is selectedfrom C₇ to C₁₇ alkyl. In some embodiments, the alkyl group is selectedfrom C₆ to C₁₂ alkyl. In some embodiments, R₂ is selected from C₇ alkyl,C₉ alkyl, C₁₁ alkyl, C₁₃ alkyl, C₁₅ alkyl, and C₁₇ alkyl. In someembodiments, R₂ is selected from C₁₃ to C₁₇ alkyl, such as from C₁₃alkyl, C₁₅ alkyl, and C₁₇ alkyl. In some embodiments, R₂ is a C₁, C₂,C₃, C₄, C₅, C₆, C₇, C₈, C₉, C₁₀, C₁₁, C₁₂, C₁₃, C₁₄, C₁₅, C₁₆, C₁₇, C₁₈,C₁₉, C₂₀, C₂₁, or C₂₂ alkyl. In certain embodiments, R₂ is saturated. Incertain embodiments, R₂ is branched.

In some embodiments, R₃ is an optionally substituted alkyl that issaturated or unsaturated, and branched or unbranched. In someembodiments, the alkyl group is a C₁ to C₄₀ alkyl, C₁ to C₂₂ alkyl or C₁to C₁₈ alkyl. In some embodiments, the alkyl group is selected from C₇to C₁₇ alkyl. In some embodiments, R₃ is selected from C₇ alkyl, C₉alkyl, C₁₁ alkyl, C₁₃ alkyl, C₁₅ alkyl, and C₁₇ alkyl. In someembodiments, R₃ is selected from C₁₃ to C₁₇ alkyl, such as from C₁₃alkyl, C₁₅ alkyl, and C₁₇ alkyl. In some embodiments, R₃ is a C₁, C₂,C₃, C₄, C₅, C₆, C₇, C₈, C₉, C₁₀, C₁₁, C₁₂, C₁₃, C₁₄, C₁₅, C₁₆, C₁₇, C₁₈,C₁₉, C₂₀, C₂₁, or C₂₂ alkyl.

In some embodiments, R₄ is an optionally substituted alkyl that issaturated or unsaturated, and branched or unbranched. In someembodiments, the alkyl group is a C₁ to C₄₀ alkyl, C₁ to C₂₂ alkyl or C₁to C₁₈ alkyl. In some embodiments, the alkyl group is selected from C₇to C₁₇ alkyl. In some embodiments, R₄ is selected from C₇ alkyl, C₉alkyl, C₁₁ alkyl, C₁₃ alkyl, C₁₅ alkyl, and C₁₇ alkyl. In someembodiments, R₄ is selected from C₁₃ to C₁₇ alkyl, such as from C₁₃alkyl, C₁₅ alkyl, and C₁₇ alkyl. In some embodiments, R₄ is a C₁, C₂,C₃, C₄, C₅, C₆, C₇, C₈, C₉, C₁₀, C₁₁, C₁₂, C₁₃, C₁₄, C₁₅, C₁₆, C₁₇, C₁₈,C₁₉, C₂₀, C₂₁, or C₂₂ alkyl.

As noted above, in certain embodiments, it may be possible to manipulateone or more of the estolides' properties by altering the length of R₁and/or its degree of saturation. However, in certain embodiments, thelevel of substitution on R₁ may also be altered to change or evenimprove the estolides' properties. Without being bound to any particulartheory, in certain embodiments, it is believed that the presence ofpolar substituents on R₁, such as one or more hydroxy groups, mayincrease the viscosity of the estolide, while increasing pour point.Accordingly, in some embodiments, R₁ will be unsubstituted or optionallysubstituted with a group that is not hydroxyl.

In some embodiments, the estolide is in its free-acid form, wherein R₂of Formula I or II is hydrogen. In some embodiments, R₂ is selected fromoptionally substituted alkyl that is saturated or unsaturated, andbranched or unbranched. In certain embodiments, the R₂ residue maycomprise any desired alkyl group, such as those derived fromesterification of the estolide with the alcohols identified in theexamples herein. In some embodiments, the alkyl group is selected fromC₁ to C₄₀, C₁ to C₂₂, C₃ to C₂₀, C₁ to C₁₈, or C₆ to C₁₂ alkyl. In someembodiments, R₂ may be selected from C₃ alkyl, C₄ alkyl, C₈ alkyl, C₁₂alkyl, C₁₆ alkyl, C₁₈ alkyl, and C₂₀ alkyl. For example, in certainembodiments, R₂ may be branched, such as isopropyl, isobutyl, or2-ethylhexyl. In some embodiments, R₂ may be a larger alkyl group,branched or unbranched, comprising C₁₂ alkyl, C₁₆ alkyl, C₁₈ alkyl, orC₂₀ alkyl. Such groups at the R₂ position may be derived fromesterification of the free-acid estolide using the Jarcol™ line ofalcohols marketed by Jarchem Industries, Inc. of Newark, N.J., includingJarcol™ I-18CG, I-20, I-12, I-16, I-18T, and 85BJ. In some cases, R₂ maybe sourced from certain alcohols to provide branched alkyls such asisostearyl and isopalmityl. It should be understood that suchisopalmityl and isostearyl akyl groups may cover any branched variationof C₁₆ and C₁₈, respectively. For example, the estolides describedherein may comprise highly-branched isopalmityl or isostearyl groups atthe R₂ position, derived from the Fineoxocol® line of isopalmityl andisostearyl alcohols marketed by Nissan Chemical America Corporation ofHouston, Tex., including Fineoxocol® 180, 180N, and 1600. Without beingbound to any particular theory, in certain embodiments, large,highly-branched alkyl groups (e.g., isopalmityl and isostearyl) at theR₂ position of the estolides can provide at least one way to increase anestolide-containing composition's viscosity, while substantiallyretaining or even reducing its pour point.

In some embodiments, the compounds described herein may comprise amixture of two or more estolide compounds of Formula I or II. It ispossible to characterize the chemical makeup of an estolide, a mixtureof estolides, or a composition comprising estolides, by using thecompound's, mixture's, or composition's measured estolide number (EN) ofcompound or composition. The EN represents the average number of fattyacids added to the base fatty acid. The EN also represents the averagenumber of estolide linkages per molecule:

EN=n+1

wherein n is the number of secondary (β) fatty acids. Accordingly, asingle estolide compound will have an EN that is a whole number, forexample for dimers, trimers, and tetramers:

-   -   dimer EN=1    -   trimer EN=2    -   tetramer EN=3

However, a composition comprising two or more estolide compounds mayhave an EN that is a whole number or a fraction of a whole number. Forexample, a composition having a 1:1 molar ratio of dimer and trimerwould have an EN of 1.5, while a composition having a 1:1 molar ratio oftetramer and trimer would have an EN of 2.5.

In some embodiments, the compositions may comprise a mixture of two ormore estolides having an EN that is an integer or fraction of an integerthat is greater than 4.5, or even 5.0. In some embodiments, the EN maybe an integer or fraction of an integer selected from about 1.0 to about5.0. In some embodiments, the EN is an integer or fraction of an integerselected from 1.2 to about 4.5. In some embodiments, the EN is selectedfrom a value greater than 1.0, 1.2, 1.4, 1.6, 1.8, 2.0, 2.2, 2.4, 2.6,2.8, 3.0, 3.2, 3.4, 3.6, 3.8, 4.0, 4.2, 4.4, 4.6, 4.8, 5.0, 5.2, 5.4,5.6 and 5.8. In some embodiments, the EN is selected from a value lessthan 1.2, 1.4, 1.6, 1.8, 2.0, 2.2, 2.4, 2.6, 2.8, 3.0, 3.2, 3.4, 3.6,3.8, 4.0, 4.2, 4.4, 4.6, 4.8, and 5.0, 5.2, 5.4, 5.6, 5.8, and 6.0. Insome embodiments, the EN is selected from 1, 1.2, 1.4, 1.6, 1.8, 2.0,2.2, 2.4, 2.6, 2.8, 3.0, 3.2, 3.4, 3.6, 3.8, 4.0, 4.2, 4.4, 4.6, 4.8,5.0, 5.2, 5.4, 5.6, 5.8, and 6.0.

As noted above, it should be understood that the chains of the estolidecompounds may be independently optionally substituted, wherein one ormore hydrogens are removed and replaced with one or more of thesubstituents identified herein. Similarly, two or more of the hydrogenresidues may be removed to provide one or more sites of unsaturation,such as a cis or trans double bond. Further, the chains may optionallycomprise branched hydrocarbon residues. For example, in some embodimentsthe estolides described herein may comprise at least one compound ofFormula II:

wherein

m is an integer equal to or greater than 1;

n is an integer equal to or greater than 0;

R₁, independently for each occurrence, is an optionally substitutedalkyl that is saturated or unsaturated, and branched or unbranched;

R₂ is selected from hydrogen and optionally substituted alkyl that issaturated or unsaturated, and branched or unbranched; and

R₃ and R₄, independently for each occurrence, are selected fromoptionally substituted alkyl that is saturated or unsaturated, andbranched or unbranched.

In certain embodiments, m is 1. In some embodiments, m is an integerselected from 2, 3, 4, and 5. In some embodiments, n is an integerselected from 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, and 12. In someembodiments, one or more R₃ differs from one or more other R₃ in acompound of Formula II. In some embodiments, one or more R₃ differs fromR₄ in a compound of Formula II. In some embodiments, if the compounds ofFormula II are prepared from one or more polyunsaturated fatty acids, itis possible that one or more of R₃ and R₄ will have one or more sites ofunsaturation. In some embodiments, if the compounds of Formula II areprepared from one or more branched fatty acids, it is possible that oneor more of R₃ and R₄ will be branched.

In some embodiments, R₃ and R₄ can be CH₃(CH₂)_(y)CH(CH₂)_(x)—, where xis, independently for each occurrence, an integer selected from 0, 1, 2,3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20, andy is, independently for each occurrence, an integer selected from 0, 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20.Where both R₃ and R₄ are CH₃(CH₂)_(y)CH(CH₂)_(x)—, the compounds may becompounds according to Formula I and III.

Without being bound to any particular theory, in certain embodiments,altering the EN produces estolide-containing compositions having desiredviscometric properties while substantially retaining or even reducingpour point. For example, in some embodiments the estolides exhibit adecreased pour point upon increasing the EN value. Accordingly, incertain embodiments, a method is provided for retaining or decreasingthe pour point of an estolide base oil by increasing the EN of the baseoil, or a method is provided for retaining or decreasing the pour pointof a composition comprising an estolide base oil by increasing the EN ofthe base oil. In some embodiments, the method comprises: selecting anestolide base oil having an initial EN and an initial pour point; andremoving at least a portion of the base oil, said portion exhibiting anEN that is less than the initial EN of the base oil, wherein theresulting estolide base oil exhibits an EN that is greater than theinitial EN of the base oil, and a pour point that is equal to or lowerthan the initial pour point of the base oil. In some embodiments, theselected estolide base oil is prepared by oligomerizing at least onefirst unsaturated fatty acid with at least one second unsaturated fattyacid and/or saturated fatty acid. In some embodiments, the removing atleast a portion of the base oil or a composition comprising two or moreestolide compounds is accomplished by use of at least one ofdistillation, chromatography, membrane separation, phase separation,affinity separation, and solvent extraction. In some embodiments, thedistillation takes place at a temperature and/or pressure that issuitable to separate the estolide base oil or a composition comprisingtwo or more estolide compounds into different “cuts” that individuallyexhibit different EN values. In some embodiments, this may beaccomplished by subjecting the base oil or a composition comprising twoor more estolide compounds to a temperature of at least about 250° C.and an absolute pressure of no greater than about 25 microns. In someembodiments, the distillation takes place at a temperature range ofabout 250° C. to about 310° C. and an absolute pressure range of about10 microns to about 25 microns.

In some embodiments, estolide compounds and compositions exhibit an ENthat is greater than or equal to 1, such as an integer or fraction of aninteger selected from about 1.0 to about 2.0. In some embodiments, theEN is an integer or fraction of an integer selected from about 1.0 toabout 1.6. In some embodiments, the EN is a fraction of an integerselected from about 1.1 to about 1.5. In some embodiments, the EN isselected from a value greater than 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6,1.7, 1.8, and 1.9. In some embodiments, the EN is selected from a valueless than 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, and 2.0.

In some embodiments, the EN is greater than or equal to 1.5, such as aninteger or fraction of an integer selected from about 1.8 to about 2.8.In some embodiments, the EN is an integer or fraction of an integerselected from about 2.0 to about 2.6. In some embodiments, the EN is afraction of an integer selected from about 2.1 to about 2.5. In someembodiments, the EN is selected from a value greater than 1.8, 1.9, 2.0,2.1, 2.2, 2.3, 2.4, 2.5, 2.6, and 2.7. In some embodiments, the EN isselected from a value less than 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6,2.7, and 2.8. In some embodiments, the EN is about 1.8, 2.0, 2.2, 2.4,2.6, or 2.8.

In some embodiments, the EN is greater than or equal to about 4, such asan integer or fraction of an integer selected from about 4.0 to about5.0. In some embodiments, the EN is a fraction of an integer selectedfrom about 4.2 to about 4.8. In some embodiments, the EN is a fractionof an integer selected from about 4.3 to about 4.7. In some embodiments,the EN is selected from a value greater than 4.0, 4.1, 4.2, 4.3, 4.4,4.5, 4.6, 4.7, 4.8, and 4.9. In some embodiments, the EN is selectedfrom a value less than 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, and5.0. In some embodiments, the EN is about 4.0, 4.2, 4.4, 4.6, 4.8, or5.0.

In some embodiments, the EN is greater than or equal to about 5, such asan integer or fraction of an integer selected from about 5.0 to about6.0. In some embodiments, the EN is a fraction of an integer selectedfrom about 5.2 to about 5.8. In some embodiments, the EN is a fractionof an integer selected from about 5.3 to about 5.7. In some embodiments,the EN is selected from a value greater than 5.0, 5.1, 5.2, 5.3, 5.4,5.5, 5.6, 5.7, 5.8, and 5.9. In some embodiments, the EN is selectedfrom a value less than 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, and6.0. In some embodiments, the EN is about 5.0, 5.2, 5.4, 5.4, 5.6, 5.8,or 6.0.

In some embodiments, the EN is greater than or equal to 1, such as aninteger or fraction of an integer selected from about 1.0 to about 2.0.In some embodiments, the EN is less than or equal to 2, such as aninteger or fraction of an integer selected from about 1.0 to about 2.0.In some embodiments, the EN is less than or equal to 1.8 or even 1.5,such as an integer or fraction of an integer selected from about 1.0 toabout 1.5. In some embodiments, the EN is a fraction of an integerselected from about 1.1 to about 1.7. In some embodiments, the EN is afraction of an integer selected from about 1.1 to about 1.5. In someembodiments, the EN is selected from a value greater than 1.0, 1.1, 1.2,1.3, 1.4, 1.5, 1.6, 1.7, 1.8, or 1.9. In some embodiments, the EN isselected from a value less than 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9,or 2.0. In some embodiments, the EN is about 1.0, 1.2, 1.4, 1.6, 1.8, or2.0. In some embodiments, the EN is greater than or equal to 1, such asan integer or fraction of an integer selected from about 1.2 to about2.2. In some embodiments, the EN is an integer or fraction of an integerselected from about 1.4 to about 2.0. In some embodiments, the EN is afraction of an integer selected from about 1.5 to about 1.9. In someembodiments, the EN is selected from a value greater than 1.0, 1.1. 1.2,1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, and 2.1. In some embodiments,the EN is selected from a value less than 1.2, 1.3, 1.4, 1.5, 1.6, 1.7,1.8, 1.9, 2.0, 2.1, and 2.2. In some embodiments, the EN is about 1.0,1.2, 1.4, 1.6, 1.8, 2.0, or 2.2.

In some embodiments, the EN is greater than or equal to 2, such as aninteger or fraction of an integer selected from about 2.8 to about 3.8.In some embodiments, the EN is an integer or fraction of an integerselected from about 2.9 to about 3.5. In some embodiments, the EN is aninteger or fraction of an integer selected from about 3.0 to about 3.4.In some embodiments, the EN is selected from a value greater than 2.0,2.1, 2.2, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.4, 3.5, 3.6, and3.7. In some embodiments, the EN is selected from a value less than 2.2,2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6,3.7, and 3.8. In some embodiments, the EN is about 2.0, 2.2, 2.4, 2.6,2.8, 3.0, 3.2, 3.4, 3.6, or 3.8.

Typically, base stocks and estolide-containing compositions exhibitcertain lubricity, viscosity, and/or pour point characteristics. Forexample, in certain embodiments, the base oils, compounds, andcompositions may exhibit viscosities that range from about 10 cSt toabout 250 cSt at 40° C., and/or about 3 cSt to about 30 cSt at 100° C.In some embodiments, the base oils, compounds, and compositions mayexhibit viscosities within a range from about 50 cSt to about 150 cSt at40° C., and/or about 10 cSt to about 20 cSt at 100° C.

In some embodiments, the estolide compounds and compositions may exhibitviscosities less than about 55 cSt at 40° C. or less than about 45 cStat 40° C., and/or less than about 12 cSt at 100° C. or less than about10 cSt at 100° C. In some embodiments, the estolide compounds andcompositions may exhibit viscosities within a range from about 25 cSt toabout 55 cSt at 40° C., and/or about 5 cSt to about 11 cSt at 100° C. Insome embodiments, the estolide compounds and compositions may exhibitviscosities within a range from about 35 cSt to about 45 cSt at 40° C.,and/or about 6 cSt to about 10 cSt at 100° C. In some embodiments, theestolide compounds and compositions may exhibit viscosities within arange from about 38 cSt to about 43 cSt at 40° C., and/or about 7 cSt toabout 9 cSt at 100° C.

In some embodiments, the estolide compounds and compositions may exhibitviscosities less than about 120 cSt at 40° C. or less than about 100 cStat 40° C., and/or less than about 18 cSt at 100° C. or less than about17 cSt at 100° C. In some embodiments, the estolide compounds andcompositions may exhibit a viscosity within a range from about 70 cSt toabout 120 cSt at 40° C., and/or about 12 cSt to about 18 cSt at 100° C.In some embodiments, the estolide compounds and compositions may exhibitviscosities within a range from about 80 cSt to about 100 cSt at 40° C.,and/or about 13 cSt to about 17 cSt at 100° C. In some embodiments, theestolide compounds and compositions may exhibit viscosities within arange from about 85 cSt to about 95 cSt at 40° C., and/or about 14 cStto about 16 cSt at 100° C.

In some embodiments, the estolide compounds and compositions may exhibitviscosities greater than about 180 cSt at 40° C. or greater than about200 cSt at 40° C., and/or greater than about 20 cSt at 100° C. orgreater than about 25 cSt at 100° C. In some embodiments, the estolidecompounds and compositions may exhibit a viscosity within a range fromabout 180 cSt to about 230 cSt at 40° C., and/or about 25 cSt to about31 cSt at 100° C. In some embodiments, the estolide compounds andcompositions may exhibit viscosities within a range from about 200 cStto about 250 cSt at 40° C., and/or about 25 cSt to about 35 cSt at 100°C. In some embodiments, the estolide compounds and compositions mayexhibit viscosities within a range from about 210 cSt to about 230 cStat 40° C., and/or about 28 cSt to about 33 cSt at 100° C. In someembodiments, the estolide compounds and compositions may exhibitviscosities within a range from about 200 cSt to about 220 cSt at 40°C., and/or about 26 cSt to about 30 cSt at 100° C. In some embodiments,the estolide compounds and compositions may exhibit viscosities within arange from about 205 cSt to about 215 cSt at 40° C., and/or about 27 cStto about 29 cSt at 100° C.

In some embodiments, the estolide compounds and compositions may exhibitviscosities less than about 45 cSt at 40° C. or less than about 38 cStat 40° C., and/or less than about 10 cSt at 100° C. or less than about 9cSt at 100° C. In some embodiments, the estolide compounds andcompositions may exhibit a viscosity within a range from about 20 cSt toabout 45 cSt at 40° C., and/or about 4 cSt to about 10 cSt at 100° C. Insome embodiments, the estolide compounds and compositions may exhibitviscosities within a range from about 28 cSt to about 38 cSt at 40° C.,and/or about 5 cSt to about 9 cSt at 100° C. In some embodiments, theestolide compounds and compositions may exhibit viscosities within arange from about 30 cSt to about 35 cSt at 40° C., and/or about 6 cSt toabout 8 cSt at 100° C.

In some embodiments, the estolide compounds and compositions may exhibitviscosities less than about 80 cSt at 40° C. or less than about 70 cStat 40° C., and/or less than about 14 cSt at 100° C. or less than about13 cSt at 100° C. In some embodiments, the estolide compounds andcompositions may exhibit a viscosity within a range from about 50 cSt toabout 80 cSt at 40° C., and/or about 8 cSt to about 14 cSt at 100° C. Insome embodiments, the estolide compounds and compositions may exhibitviscosities within a range from about 60 cSt to about 70 cSt at 40° C.,and/or about 9 cSt to about 13 cSt at 100° C. In some embodiments, theestolide compounds and compositions may exhibit viscosities within arange from about 63 cSt to about 68 cSt at 40° C., and/or about 10 cStto about 12 cSt at 100° C.

In some embodiments, the estolide compounds and compositions may exhibitviscosities greater than about 120 cSt at 40° C. or greater than about130 cSt at 40° C., and/or greater than about 15 cSt at 100° C. orgreater than about 18 cSt at 100° C. In some embodiments, the estolidecompounds and compositions may exhibit a viscosity within a range fromabout 120 cSt to about 150 cSt at 40° C., and/or about 16 cSt to about24 cSt at 100° C. In some embodiments, the estolide compounds andcompositions may exhibit viscosities within a range from about 130 cStto about 160 cSt at 40° C., and/or about 17 cSt to about 28 cSt at 100°C. In some embodiments, the estolide compounds and compositions mayexhibit viscosities within a range from about 130 cSt to about 145 cStat 40° C., and/or about 17 cSt to about 23 cSt at 100° C. In someembodiments, the estolide compounds and compositions may exhibitviscosities within a range from about 135 cSt to about 140 cSt at 40°C., and/or about 19 cSt to about 21 cSt at 100° C. In some embodiments,the estolide compounds and compositions may exhibit viscosities of about1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20,21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 32, 34, 36, 38, 40, 42, 44, 46,48, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 110, 120, 130, 140,150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280,290, 300, 350, or 400 cSt. at 40° C. In some embodiments, the estolidecompounds and compositions may exhibit viscosities of about 1, 2, 3, 4,5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23,24, 25, 26, 27, 28, 29, and 30 cSt at 100° C.

In some embodiments, the estolide compounds and compositions may exhibitviscosities less than about 200, 250, 300, 350, 400, 450, 500, or 550cSt at 0° C. In some embodiments, the estolide compounds andcompositions may exhibit a viscosity within a range from about 200 cStto about 250 cSt at 0° C. In some embodiments, the estolide compoundsand compositions may exhibit a viscosity within a range from about 250cSt to about 300 cSt at 0° C. In some embodiments, the estolidecompounds and compositions may exhibit a viscosity within a range fromabout 300 cSt to about 350 cSt at 0° C. In some embodiments, theestolide compounds and compositions may exhibit a viscosity within arange from about 350 cSt to about 400 cSt at 0° C. In some embodiments,the estolide compounds and compositions may exhibit a viscosity within arange from about 400 cSt to about 450 cSt at 0° C. In some embodiments,the estolide compounds and compositions may exhibit a viscosity within arange from about 450 cSt to about 500 cSt at 0° C. In some embodiments,the estolide compounds and compositions may exhibit a viscosity within arange from about 500 cSt to about 550 cSt at 0° C. In some embodiments,the estolide compounds and compositions may exhibit viscosities of about100, 125, 150, 175, 200, 225, 250, 275, 300, 325, 350, 375, 400, 425,450, 475, 500, 525, or 550 cSt at 0° C.

In some embodiments, estolide compounds and compositions may exhibitdesirable low-temperature pour point properties. In some embodiments,the estolide compounds and compositions may exhibit a pour point lowerthan about −20° C., about −25° C., about −35° C., −40° C., or even about−50° C. In some embodiments, the estolide compounds and compositionshave a pour point of about −25° C. to about −45° C. In some embodiments,the pour point falls within a range of about −30° C. to about −40° C.,about −34° C. to about −38° C., about −30° C. to about −45° C., −35° C.to about −45° C., 34° C. to about −42° C., about −38° C. to about −42°C., or about 36° C. to about −40° C. In some embodiments, the pour pointfalls within the range of about −27° C. to about −37° C., or about −30°C. to about −34° C. In some embodiments, the pour point falls within therange of about −25° C. to about −35° C., or about −28° C. to about −32°C. In some embodiments, the pour point falls within the range of about−28° C. to about −38° C., or about −31° C. to about −35° C. In someembodiments, the pour point falls within the range of about −31° C. toabout −41° C., or about −34° C. to about −38° C. In some embodiments,the pour point falls within the range of about −40° C. to about −50° C.,or about −42° C. to about −48° C. In some embodiments, the pour pointfalls within the range of about −50° C. to about −60° C., or about −52°C. to about −58° C. In some embodiments, the upper bound of the pourpoint is less than about −35° C., about −36° C., about −37° C., about−38° C., about −39° C., about −40° C., about −41° C., about −42° C.,about −43° C., about −44° C., or about −45° C. In some embodiments, thelower bound of the pour point is greater than about −70° C., about −69°C., about −68° C., about −67° C., about −66° C., about −65° C., about−64° C., about −63° C., about −62° C., about −61° C., about −60° C.,about −59° C., about −58° C., about −57° C., about −56° C., −55° C.,about −54° C., about −53° C., about −52° C., −51, about −50° C., about−49° C., about −48° C., about −47° C., about −46° C., or about −45° C.

In addition, in certain embodiments, the estolides may exhibit decreasedIodine Values (IV) when compared to estolides prepared by other methods.IV is a measure of the degree of total unsaturation of an oil, and isdetermined by measuring the amount of iodine per gram of estolide(cg/g). In certain instances, oils having a higher degree ofunsaturation may be more susceptible to creating corrosiveness anddeposits, and may exhibit lower levels of oxidative stability. Compoundshaving a higher degree of unsaturation will have more points ofunsaturation for iodine to react with, resulting in a higher IV. Thus,in certain embodiments, it may be desirable to reduce the IV ofestolides in an effort to increase the oil's oxidative stability, whilealso decreasing harmful deposits and the corrosiveness of the oil.

In some embodiments, estolide compounds and compositions describedherein have an IV of less than about 40 cg/g or less than about 35 cg/g.In some embodiments, estolides have an IV of less than about 30 cg/g,less than about 25 cg/g, less than about 20 cg/g, less than about 15cg/g, less than about 10 cg/g, or less than about 5 cg/g. In someembodiments, estolides have an IV of about 0 cg/g. The IV of acomposition may be reduced by decreasing the estolide's degree ofunsaturation. This may be accomplished by, for example, by increasingthe amount of saturated capping materials relative to unsaturatedcapping materials when synthesizing the estolides. Alternatively, incertain embodiments, IV may be reduced by hydrogenating estolides havingunsaturated caps.

In some embodiments, the estolide compounds described herein may beuseful as base oil in lubricant compositions, such as engine oilformulations. In certain embodiments, the estolide base oil comprisesgreater than 0% to about 95% by weight of the overall composition, suchas about 5% to about 90%, about 5% to about 85%, about 10% to about 75%,about 10% to about 50%, about 15% to about 65%, about 20% to about 55%,about 25% to about 60%, about 25% to about 55%, about 25% to about 40%,about 30% to about 40%, about 30% to about 45%, about 32% to about 38%,or even about 33% to about 36% by weight of the composition. In certainembodiments, the estolide base oil comprises at least 25% by weight ofthe composition.

In certain embodiments, the composition further comprises at least onenon-estolide base oil. In certain embodiments, the at least onenon-estolide base oil is selected from a mineral oil, a synthetic oil,or a semi-synthetic oil. Exemplary mineral oils include, but are notlimited to, base stocks referred to as Group I (solvent refined mineraloils) and Group II (hydro cracked mineral oils) oils. Exemplarysemi-synthetic oils include, but are not limited to, Group III (severelyhydro cracked oil) oils. Exemplary synthetic oils include, but are notlimited to, esters, polyolefins, and naphthenes. In certain embodiments,the at least one non-estolide comprises greater than 0% to about 95% byweight of the overall composition, such as about 5% to about 85%, about10% to about 75%, about 15% to about 70%, about 15% to about 65%, about20% to about 55%, about 25% to about 55%, about 30% to about 65%, about30% to about 45%, about 40% to about 55%, or even about 32% to about 38%by weight of the composition.

In certain embodiments, the at least one non-estolide base oil is amineral oil. Exemplary mineral oils include, but are not limited to,white mineral oils, paraffinic oils, and naphthenic oils, such as GroupI and Group II paraffinic oils

In certain embodiments, the composition comprises a synthetic oilselected from one or more of hydrocarbon oils and halo-substitutedhydrocarbon oils such as polymerized and interpolymerized olefins (e.g.,polybutylenes, polypropylenes, propylene-isobutylene copolymers,chlorinated polybutylenes, poly(1-octenes), or poly(1-decenes));alkylbenzenes (e.g., dodecylbenzenes, tetradecylbenzenes,dinonylbenzenes, or di-(2-ethylhexyl)benzenes); polyphenyls (e.g.,biphenyls, terphenyls, or alkylated polyphenyl), alkylated diphenylethers, alkylated diphenyl sulfides, and the derivatives, analogs orhomologs thereof. In certain embodiments, the synthetic oil is apolyalphaolefin (PAO). Exemplary PAOs include, but are not limited to,PAO2, PAO4, PAO6, PAO8, PAO9, PAO10, PAO40, and PAO100.

In certain embodiments, the synthetic oil comprises one or more alkyleneoxide polymers and interpolymers and derivatives thereof, wherein theterminal hydroxyl groups have been modified by esterification oretherification. Exemplary oils may be prepared through polymerization ofethylene oxide or propylene oxide, the alkyl and aryl ethers of thesepolyoxyalkylene polymers (e.g., methylpolyisopropylene glycol etherhaving an average molecular weight of about 1000, diphenyl ether ofpolyethylene glycol have a molecular weight of about 500 to about 1000,diethyl ether of polypropylene glycol having a molecular weight of about1000 to about 1500), or mono- and polycarboxylic esters thereof, forexample, acetic acid esters, mixed C₃-C₈ fatty acid esters, or diestersof tetraethylene glycol.

In certain embodiments, the synthetic oil is a non-estolide ester.Exemplary esters include, but are not limited to, esters of dicarboxylicacids (e.g., phthalic acid, succinic acid, alkyl succinic acids andalkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacicacid, fumaric acid, adipic acid, or alkenyl malonic acids) with anysuitable alcohol (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol,2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, orpropylene glycol). Exemplary esters include dibutyl adipate,di(2-ethylhexyl) sebacate, di-hexyl fumarate, dioctyl sebacate,diisooctyl azelate, diisodecyl azealate, dioctyl phthalate, didecylphthalate, dicicosyl sebacate, the 2-ethylhexyl diester of linoleic aciddimer, and the complex ester formed by reacting one mole of sebacic acidwith two moles of tetraethylene glycol and two moles of 2-ethylhexanoicacid.

In certain embodiments, the synthetic oil is a polyol ester made fromone or more esters derived from C₅ to C₁₂ monocarboxylic acids andpolyols and polyol ethers such as neopentyl glycol, trimethylolpropane,pentaerythritol, dipentaerythritol, and tripentaerythritol. Othersynthetic oils include liquid esters of phosphorus-containing acids(e.g., tricresyl phosphate, trioctyl phosphate, and the diethyl ester ofdecylphosphonic acid), and polymeric tetrahydrofurans.

In certain embodiments, the at least one non-estolide base oil is asemi-synthetic oil. In certain embodiments, the semi-synthetic oil is amineral oil that has been subjected to hydrogenation or hydrocrackingunder special conditions to remove, e.g., undesirable chemicalcompositions and impurities to provide a base oil having synthetic oilcomponents and properties. In certain embodiments, the semi-syntheticoil is a Group III petroleum base oil. In certain embodiments, the GroupIII oil has a sulfur level less than 0.03%, with saturates greater thanor equal to 90% and a viscosity index of greater than or equal to 120.Exemplary Group III oils include, but are not limited to, the Yubase®line of products marketed by SK Lubricants Co., Ltd., such as Yubase 4,Yubase 5, Yubase 6, and Yubase 8.

In certain embodiments, the composition comprises one or more estolidecompounds and a lubricant additive package containing one or moreadditional additives. Exemplary additive packages may include one ormore components selected from solvents, viscosity index improvers,corrosion inhibitors, oxidation inhibitors, dispersants, lube oil flowimprovers, detergents and rust inhibitors, pour point depressants,anti-foaming agents, antiwear agents, seal swellants, or frictionmodifiers.

In some cases, dissolution of the additives into the base oil may befacilitated by solvents and by mixing accompanied with mild heating. Insome embodiments, the compositions described herein can employ greaterthan 0 wt. % up to about 95 wt. % of the additive package, with theremainder being the estolide base oil. In some embodiments, the estolidebase oil may comprise from about 1 to about 95 wt. %, about 10 to about80 wt. %, about 25 to about 75 wt. %, about 30 to about 60 wt. %, orabout 40 to about 50 wt. % of the composition.

Unless otherwise indicated, all of the weight percentages expressedherein is based on the content of the overall composition, which will bethe sum of the additives plus the weight of the base oil(s).

In certain embodiments, the composition comprises at least one corrosioninhibitor. Corrosion inhibitors, also known as anti-corrosive agents,reduce the degradation of the metallic parts contacted by thelubricating oil composition. Illustrative of corrosion inhibitors arephosphosulfurized hydrocarbons and the products obtained by reaction ofa phosphosulfurized hydrocarbon with an alkaline earth metal oxide orhydroxide, optionally in the presence of an alkylated phenol or of analkylphenol thioester, and also optionally in the presence of carbondioxide.

In certain embodiments, the composition comprises further at least oneantioxidant. Oxidation inhibitors, or antioxidants, reduce the tendencyof base oils to deteriorate in service which deterioration can beevidenced by the products of oxidation such as sludge and varnish-likedeposits on the metal surfaces, and by viscosity growth. Such oxidationinhibitors include alkaline earth metal salts of alkyl-phenolthioestershaving, for example, C₅ to C₁₂ alkyl side chains, such as calciumnonylphenol sulfide, barium t-octylphenol sulfide, dioctylphenylamine,phenylalphanaphthylamine, or phosphosulfurized or sulfurizedhydrocarbons. Also included are oil soluble antioxidant copper compoundssuch as copper salts of C₁₀-C₁₈ oil soluble fatty acids. In certainembodiments, the at least one antioxidant is selected from phenolicantioxidants, amine antioxidants, or organometallic antioxidants. Incertain embodiments, the at least one antioxidant is a phenolicantioxidant. In certain embodiments, the at least one antioxidant is ahindered phenolic antioxidant. In certain embodiments, the at least oneantioxidant is an amine antioxidant, such as a diarylamine, benzylamine,or polyamine. In certain embodiments, the at least one antioxidant is adiarylamine antioxidant, such as an alkylated diphenylamine antioxidant.In certain embodiments, the at least one antioxidant is aphenyl-α-naphthylamine or an alkylated phenyl-α-naphthylamine. Incertain embodiments, the at least one antioxidant comprises anantioxidant package. In certain embodiments, the antioxidant packagecomprises one or more phenolic antioxidants and one or more amineantioxidants, such as a combination of a hindered phenolic antioxidantand an alkylated diphenylamine antioxidant. In some embodiments, theantioxidant may be present in amounts of about 0% to about 10% byweight, or about 0% to about 5% by weight of the composition, such asabout 0.01% to about 3%, about 0.1% to about 2%, or about 0.5% to about1.5%. In certain embodiments, the antioxidant comprises at least 0.1% byweight of the composition.

In certain embodiments, the composition further comprises at least onefriction modifier. Representative examples of suitable frictionmodifiers may include fatty acid esters and amides, molybdenum complexesof polyisobutenyl succinic anhydride-amino alkanols, glycerol esters ofdimerized fatty acids, alkane phosphonic acid salts, phosphonate with anoleamide, S-carboxyalkylene hydrocarbyl succinimide,N(hydroxylalkyl)alkenylsuccinamic acids or succinimides, di-(loweralkyl) phosphites and epoxides, and alkylene oxide adduct ofphosphosulfurized N(hydroxyalkyl)alkenyl succinimides. Suitable frictionmodifiers may include succinate esters, or metal salts thereof, ofhydrocarbyl substituted succinic acids or anhydrides andthiobis-alkanols.

In certain embodiments, the composition further comprises at least onedispersant. Dispersants may be used to maintain oil insolubles,resulting from oxidation during use, in suspension in the fluid thuspreventing sludge flocculation and precipitation or deposition on metalparts. Suitable dispersants may include high molecular weight alkylsuccinimides, the reaction product of oil-soluble polyisobutylenesuccinic anhydride with ethylene amines such as tetraethylene pentamineand borated salts thereof.

Dispersants of the ashless type can also be used in the compositionsdescribed herein. An exemplary ashless dispersant is a derivatizedhydrocarbon composition which is mixed with at least one of amine,alcohol, including polyol, or aminoalcohol. Derivatized hydrocarbondispersants may be the product of reacting (1) a functionalizedhydrocarbon of less than 500 Mn (number average molecular weight)wherein functionalization comprises at least one group of the formula—CO—Y—R₃ wherein Y is O or S; R₃ is H, hydrocarbyl, aryl, substitutedaryl or substituted hydrocarbyl and wherein at least 50 mole % of thefunctional groups are attached to a tertiary carbon atom; and (2) anucleophilic reactant; wherein at least about 80% of the functionalgroups originally present in the functionalized hydrocarbon arederivatized.

In certain embodiments, the composition further comprises at least onepour-point depressant. Pour-point depressants, also known as lube oilflow improvers, can lower the temperature at which the fluid will flow.Exemplary additives include C₈-C₁₈ dialkyl fumarate vinyl acetatecopolymers, polymethacrylates and wax naphthalene. In certainembodiments, the at least one pour-point depressant comprises about 0.01to about 1% by weight of the composition, such as about 0.1 to about0.5%.

In certain embodiments, the composition further comprises at least onefoam control (antifoam) agent. Foam control can also be provided by ananti-foamant of the polysiloxane type such as silicone oil andpolydimethyl siloxane.

In certain embodiments, the composition further comprises at least oneanti-wear agent. Anti-wear agents reduce wear of metal parts, andrepresentative materials include zinc alkyl dithiophosphates such asdialkyldithiophosphate, and zinc diaryl diphosphates. Also included areashless zinc replacements, including boron-type antiwear compounds.Exemplary ashless boron-type compounds include, but are not limited to,borated nitrogen compounds such as a borated polyalkenyl succinimide.

In certain embodiments, the composition further comprises at least onedetergent and/or metal rust inhibitor (“Detergent inhibitor”).Detergents and metal rust inhibitors include the metal salts of sulfonicacids, alkylphenols, sulfurized alkylphenols, alkyl salicylates,naphthenates and other oil soluble mono- and dicarboxylic acids.Exemplary sulfonates include metal salts of optionally substitutedcarbocyclic sulfonic acids, optionally substituted aryl sulfonic acids,or aliphatic sulfonic acids. In certain embodiments, the detergentinhibitor comprises a metal salt of an alkylaryl sulfonic acid, such asa calcium long-chain alkylaryl sulfonate. Neutral or highly basic metalsalts such as highly basic alkaline earth metal sulfonates (such ascalcium and magnesium salts) may be used as such detergents. In certainembodiments, the detergent inhibitor comprises a calcium detergent, suchas a calcium sulfonate, a calcium phenate, or a calcium salicylate. Incertain embodiments, the detergent inhibitor is an overbased detergent,such as an overbased calcium compound. In certain embodiments, thedetergent inhibitor has a total base number of about 25 to about 600,such as about 30 to about 60, about 40 to about 80, about 100 to about500, or about 150 to about 450, as expressed in mg KOH/g of thedetergent composition. In certain embodiments, the detergent inhibitoris a nonylphenol sulfide. Exemplary materials may be prepared byreacting an alkylphenol with commercial sulfur dichlorides. Suitablealkylphenol sulfides can also be prepared by reacting alkylphenols withelemental sulfur. Other suitable detergent inhibitors may includeneutral and basic salts of phenols, generally known as phenates, whereinthe phenol is generally an alkyl substituted phenolic group, where thesubstituent is an aliphatic hydrocarbon group having about 4 to 400carbon atoms. Exemplary detergent inhibitors may include, for example,“S911” and “P5710” sold by Infineum USA of Linden, N.J. In someembodiments, the detergent inhibitor comprises from about 0.1 wt. % toabout 20 wt. %, about 2 wt. % to about 18 wt. %, about 5 wt. % to about15 wt. %, or about 11 wt. % to about 13 wt. % of the composition. Insome embodiments, the detergent inhibitor comprises at least 10 wt. % ofthe composition.

In certain embodiments, the composition further comprises at least oneviscosity modifier. Viscosity modifiers may impart high and lowtemperature operability to the lubricating oil and permit it to remainshear stable at elevated temperatures and also exhibit acceptableviscosity or fluidity at low temperatures. Exemplary viscosity modifiersmay include high molecular weight hydrocarbon polymers includingpolyesters. The viscosity modifiers may also be derivatized to includeother properties or functions, such as the addition of dispersancyproperties. Representative examples of suitable viscosity modifiersinclude: polybutenes; polyisobutylenes (PIB); copolymers of ethylene andpropylene; polymethacrylates; methacrylate copolymers; copolymers of anunsaturated dicarboxylic acid and vinyl compound; styrene-type polymersincluding, but not limited to, interpolymers of styrene and acrylicesters, and copolymers of styrene/isoprene, and/or styrene/butadiene,and partially-hydrogenated variants thereof; and isoprene/butadiene,such as the partially hydrogenated homopolymers of butadiene andisoprene. Exemplary viscosity modifiers include styrene-diene typepolymers, such as the SV277 viscosity modifier additive sold by InfineumUSA of Linden, N.J. In some embodiments, the at least one viscositymodifier comprises from about 0 wt. % to about 75 wt. % or about 5 wt. %to about 60 wt. % of the composition, such as about 0.1 wt. % to about15 wt. %, about 1 wt. % to about 10 wt. %, or about 2 wt. % to about 5wt. % of the composition. In some embodiments, the viscosity modifiercomprises at least 10 wt. % of the composition.

In some embodiments, the compositions comprise at least one polybutenepolymer. In some embodiments, the polybutene may comprise a mixture ofpoly-n-butenes and polyisobutylene, which may result from thepolymerization of C₄ olefins and generally will have a number averagemolecular weight of about 300 to 1500, or a polyisobutylene orpolybutene having a number average molecular weight of about 400 to1300. In some embodiments, the polybutene and/or polyisobutylene mayhave a number average molecular weight of about 950 Mn may be measuredby gel permeation chromatography. Polymers composed of 100%polyisobutylene or 100% poly-n-butene should be understood to fallwithin the scope of this disclosure and within the meaning of the term“a polybutene polymer”. An exemplary polyisobutylene includes “PIBS1054” which has an Mn of about 950 and is sold by Infineum USA ofLinden, N.J.

In some embodiments, the at least one polybutene polymer comprises amixture of polybutenes and polyisobutylene prepared from a C₄ olefinrefinery stream containing about 6 wt. % to about 50 wt. % isobutylenewith the balance a mixture of butene (cis- and trans-) isobutylene andless than 1 wt %. butadiene. For example, the polymer may be preparedvia Lewis acid catalysis from a C₄ stream composed of 6-45 wt. %isobutylene, 25-35 wt. % saturated butenes and 15-50 wt. % 1- and2-butenes.

In certain embodiments, the composition further comprises at least onesolvent. Suitable solvents may generally be characterized as beingnormally liquid petroleum or synthetic hydrocarbon solvents having aboiling point not higher than about 300° C. at atmospheric pressure.Such a solvent may also have a flash point in the range of about 60-120°C. Typical examples include kerosene, hydrotreated kerosene, middledistillate fuels, isoparaffinic and naphthenic aliphatic hydrocarbonsolvents, dimers, and higher oligomers of propylene butene and similarolefins as well as paraffinic and aromatic hydrocarbon solvents andmixtures thereof. Such solvents may contain functional groups other thancarbon and hydrogen provided such groups do not adversely affectperformance of the composition. Suitable solvents include naphthenictype hydrocarbon solvents having a boiling point range of about 91.1° C.to about 113.9° C., such as “Exxsol D80” sold by Exxon Chemical Company.In some embodiments, the composition comprises from about 0 wt. % toabout 75 wt. %, about 5 wt. % to about 60 wt. %, about 10 wt. % to about50 wt. %, about 15 wt. % to about 40 wt. %, about 20 wt. % to about 30wt. %, or about 23 wt. % to about 27 wt. % of the at least one solvent.

In certain embodiments, the composition comprises an estolide base oilhaving a kinematic viscosity equal to or less than about 12 cSt whenmeasured at 100° C. In certain embodiments, the composition comprises anestolide base oil having a kinematic viscosity equal to or less thanabout 11 cSt when measured at 100° C. In certain embodiments, thecomposition comprises an estolide base oil having a kinematic viscosityequal to or less than about 10 cSt when measured at 100° C., such asabout 1 to about 10, about 2 to about 9, about 4 to about 9, or about 5to about 10 cSt at 100° C.

In certain embodiments, the estolide base oil comprises the balance ofthe composition after addition of the components of the additivepackage. In certain embodiments, the estolide base oil comprises about 1to about 95% by weight of the composition, such as about 1 to about 69wt. %, about 15 to about 65 wt. %, about 25 to about 60 wt. %, about 35to about 55 wt. %, about 40 to about 50 wt. %, or about 42 to about 46wt. %.

The present disclosure is based on the surprising discovery that certaincombinations of additive packages and estolide base stocks can provideengine oil compositions exhibiting properties that meet or exceedcertain guidelines for the lubricant quality and performance accordingto the American Petroleum Institute (API), including InternationalLubricant Standardization and Approval Committee (ILSAC) GF-5 limits setfor Sequence IIIG, Sequence VG, Sequence IVA, Sequence VIII, and/orSequence VID testing conditions.

The Sequence IIIG is a fired engine test designed to evaluate acandidate oil's performance in three areas: viscosity increase; hightemperature piston deposits; and valve train wear. For GF-5, theperformance parameters are: viscosity increase as a percentage of newoil (PVISFNL); viscosity; weighted piston deposits; cam and lifter wear(ACLWFNL); and hot stuck rings. The Sequence IIIG testing is conductedusing ASTM Method D7320 as follows:

Engine GM 3.8 L (3800 cc) V-6 Test length (h) 100 Speed (rpm) 3600 Load(Nm) 250 Oil Temp. (° C.) 155 Coolant Temp. (° C.) 115 Intake Air Temp.(° C.) 35 Valve Spring Load (lbs) 205 @ 0.375 inch deflection Air/FuelRatio 15:1 Initial Oil Charge (mL) 5500 Oil check and samples (h) 0, 20,40, 60, 80, and 100 Camshaft Nodular cast iron (phosphate) Cam BushingBabbit Lifters Alloy cast iron Fuel Haltermann fuel unleaded

Sequence IIIGA testing merits include those that measure for lowtemperature used oil viscosity (MRV) and used oil cold crank simulator(CCS), per ASTM Method 7528. Sequence IIIGB testing merits include thatfor phosphorous retention, per ASTM Method 7320. In certain embodiments,the engine oil compositions described herein meet or exceed one or moreof the GF-5 limits set for certain Sequence IIIG testing procedures. Incertain embodiments, the formulations meet or exceed all of the GF-5performance limits described herein.

In certain embodiments, the composition may exhibit an ACLWFNL WearRating (m) of 60 or less, such as ≦50, ≦40, ≦35, ≦25, ≦15, or even ≦10.In certain embodiments, the compositions described may exhibit anACLWFNL Wear Rating (m) of about 0 to about 60, such as about 0 to about30, about 1 to about 25, about 5 to about 20, about 5 to about 15, oreven about 10 to about 15.

In certain embodiments, the composition may exhibit a PVISFNL ViscosityIncrease (% @ 40° C.) of 150 or less, such as ≦125, ≦100, ≦85, ≦65, oreven ≦50. In certain embodiments, the compositions described may exhibita PVISFNL Viscosity Increase (% @ 40° C.) of about 0 to about 150, suchas about 10 to about 125, such as about 5 to about 100, about 25 toabout 100, such as about 25 to about 85, about 35 to about 85, about 45to about 65, or even about 40 to about 60.

In certain embodiments, the composition may exhibit a Weighted PistonDeposit (merits) of ≧4, ≧5, ≧6, ≧7, ≧8, or ≧9. In certain embodiments,the compositions described may exhibit a Weighted Piston Deposit(merits) of about 6.5 to about 10, such as about 7 to about 9.5, about 8to about 9, or even about 8.2 to about 8.8.

In certain embodiments, the composition may exhibit IIIGB—PhosphorousRetention of ≧80%, ≧85%, or ≧90%. In some embodiments, the compositionsdescribed may exhibit IIIGB—Phosphorous Retention of about 80% to about100%, such as about 80% to about 90%.

In certain embodiments, the composition may exhibit IIIGA—Used Oil MRV(cP @-30° C.) of 60,000 or less, such as ≦50,000, ≦40,000, ≦30,000,≦25,000, or even ≦20,000. In certain embodiments, the compositionsdescribed may exhibit IIIGA—Used Oil MRV (cP @ −30° C.) of about 5,000to about 50,000, such as about 10,000 to about 40,000, about 15,000 toabout 35,000, or about 20,000 to about 30,000.

In certain embodiments, the composition may exhibit IIIGA—Used Oil CCS(cP @-25° C.) of 7,000 or less, such as ≦6,500, ≦6,000, ≦5,000, ≦4,000,or even ≦3,000. In certain embodiments, the compositions described mayexhibit IIIGA—Used Oil MRV (cP @ −25° C.) of about 2,000 to about 7,000,such as about 4,000 to about 7,000, about 5,000 to about 7,000, or about6,000 to about 6,800.

The Sequence VG is a fired engine test designed to evaluate a candidateoil's performance in three areas: wear; sludge; and varnish. For GF-5,the performance parameters are evaluated per ASTM Method D6593 for:engine sludge; rocker cover sludge; engine varnish; piston skirtvarnish; oil screen sludge; oil screen debris; hot stuck compressionrings; cold stuck rings; and oil ring clogging. The test engine is aFord 4.6 L, spark ignition, four-stroke, eight-cylinder V configurationengine. Features of this engine include an overhead camshaft, across-flow fast-burn cylinder head design, two valves per cylinder andelectronic port fuel injection. It is based on the Ford Motor Co. 4.6 LEFI Crown Victoria passenger car engine. In certain embodiments, theengine oil compositions described herein meet or exceed one or more ofthe GF-5 limits set for certain Sequence VG testing procedures. Incertain embodiments, the formulations meet or exceed all of the GF-5performance limits described herein.

In certain embodiments, the composition may exhibit an average enginesludge (merits) rating of ≧8, ≧10, ≧12, ≧13, ≧14, or ≧15. In certainembodiments, the compositions described may exhibit an average enginesludge (merits) of about 8 to about 20, such as about 8.5 to about 15,about 9 to about 13, or even about 9.5 to about 12.5.

In certain embodiments, the composition may exhibit an average rockercover sludge (merits) rating of ≧8.3, ≧8.5, ≧9, ≧9.5, ≧10, or ≧11. Incertain embodiments, the compositions described may exhibit an averagerocker cover sludge (merits) of about 8.3 to about 12, such as about 8.5to about 11, about 8.8 to about 10, or even about 9 to about 9.5.

In certain embodiments, the composition may exhibit an average enginevarnish (merits) rating of ≧8.9, ≧9.2, ≧9.5, ≧9.8, ≧10, or ≧10.5. Incertain embodiments, the compositions described may exhibit an averageengine varnish (merits) of about 8.9 to about 12, such as about 9.1 toabout 10.5, about 9.3 to about 10, or even about 9.5 to about 9.8.

In certain embodiments, the composition may exhibit an average pistonskirt varnish (merits) rating of ≧7.5, ≧7.7, ≧8, ≧8.2, ≧8.5, or ≧9. Incertain embodiments, the compositions described may exhibit an averagepiston skirt varnish (merits) of about 7.5 to about 12, such as about7.8 to about 10, about 8 to about 9.5, or even about 8.2 to about 8.8.

In certain embodiments, the composition may exhibit an oil screen sludge(% area) rating of 15% or less, such as ≦13%, ≦11%, ≦8%, ≦7%, or even≦5%. In certain embodiments, the compositions described may exhibit anoil screen sludge (% area) of about 0.1% to about 15%, such as about 2%to about 13%, about 4% to about 11%5, or even about 6% to about 9%.

In certain embodiments, the composition may exhibit an oil screen debris(% area) rating of 15% or less, such as ≦13%, ≦11%, ≦8%, ≦7%, or even≦5%. In certain embodiments, the compositions described may exhibit anoil screen debris (% area) of about 0.1% to about 15%, such as about 2%to about 13%, about 4% to about 11%5, or even about 6% to about 9%.

In certain embodiments, the composition may exhibit no hot stuckcompression rings and/or cold stuck rings. In certain embodiments, thecomposition may exhibit an oil ring clogging (% area) rating of 15% orless, such as ≦13%, ≦11%, ≦8%, ≦7%, or even ≦5%. In certain embodiments,the compositions described may exhibit an oil ring clogging (% area) ofabout 0.1% to about 15%, such as about 2% to about 13%, about 4% toabout 11%5, or even about 6% to about 9%.

The Sequence IVA is a fired engine test designed to evaluate a candidateoil's performance in valvetrain wear. For GF-5, the performanceparameters are evaluated per ASTM Method D6891 for a lubricant's abilityto protect against cam lobe wear for overhead valve train equippedengines with sliding cam followers. The Sequence IVA uses a Nissan KA24Eengine: 24 L displacement, water-cooled, fuel-injected, four cylinderin-line overhead camshaft. In certain embodiments, the engine oilcompositions described herein meet or exceed one or more of the GF-5limits set for certain Sequence IVA testing procedures. In certainembodiments, the formulations meet or exceed all of the GF-5 performancelimits described herein. In certain embodiments, the compositionsdescribed herein exhibit an average cam wear (7 position average, μm) of90 or less, such as ≦50, ≦30, ≦25, ≦15, ≦10, or even ≦5. In certainembodiments, the compositions described may exhibit an cam wear (7position average, μm) of about 0 to about 90, such as about 0.1 to about30, about 0.4 to about 25, about 0.6 to about 10, about 0.8 to about 5,or even about 1 to about 2.

The Sequence VIII is a fired engine test designed to evaluate acandidate oil's performance in bearing corrosion and shear stability.For GF-5, the performance parameters are evaluated per ASTM Method D6709for a lubricant's ability to protect engines against bearing weightloss. This method covers SAE grades 5W, 10W, 20, 30, 40, and 50, as wellas multi-viscosity grades, used in spark ignition engines. An oil isevaluated for its ability to protect the engine and oil fromdeterioration under high-temp and severe service conditions. TheSequence VIII uses a carbureted, spark ignition Cooperative LubricationResearch oil test engine run on unleaded fuel. In certain embodiments,the engine oil compositions described herein meet or exceed one or moreof the GF-5 limits set for certain Sequence VIII testing procedures. Incertain embodiments, the formulations meet or exceed all of the GF-5performance limits described herein.

In certain embodiments, the compositions described herein exhibit a10-hour stripped kinematic viscosity (@ 100° C., cSt) of 9.3 or more,such as ≧9.4, ≧9.5, ≧9.8, ≧10, ≧10.2, or even ≧10.5. In certainembodiments, the compositions described may exhibit a 10-hour strippedkinematic viscosity (@ 100° C., cSt) of about 9.3 to about 15, such asabout 9.4 to about 11, about 9.5 to about 10.5, or even about 9.8 toabout 10.2.

The Sequence VID is a fired engine test designed to evaluate a candidateoil's effect on fuel efficiency. For GF-5, the performance parametersare evaluated per ASTM Method D7589 for the effects of automotive engineoils on the fuel economy of passenger cars and light-duty (3856 kg, 8500pounds or less gross vehicle weight) trucks. The Sequence VID uses a2008 3.6 L V6 General Motors gasoline engine equipped with an externaloil heating/cooling system and a “flying flush” system for changing oilswithout an engine shutdown is used for this test. In certainembodiments, the engine oil compositions described herein meet or exceedone or more of the GF-5 limits set for certain Sequence VID testingprocedures. In certain embodiments, the formulations meet or exceed allof the GF-5 performance limits described herein.

In certain embodiments, the compositions described herein (SAE 5W-30viscosity grade) exhibit an FEI summary of at least 1.9% after 60 hours.In certain embodiments, the compositions described herein (SAE 5W-30viscosity grade) exhibit an FEI after 60 hours of aging (%) of at least1.9, such as ≧1.9, ≧2, ≧2.5, ≧3, ≧3.5, or even ≧4. In certainembodiments, the compositions described herein (SAE 5W-30 viscositygrade) exhibit an FEI after 60 hours of aging (%) of about 1.9 to about5, such as about 2 to about 4.5, about 2.5 to about 4, or even about 3to about 3.5.

In certain embodiments, the compositions described herein (SAE 5W-30viscosity grade) exhibit an FEI summary of at least 0.9% after 100hours. In certain embodiments, the compositions described herein (SAE5W-30 viscosity grade) exhibit an FEI 2 after 100 hours of aging (%) ofat least 0.9, such as ≧0.9, ≧1, ≧1.2, ≧1.5, ≧2, or even ≧2.5. In certainembodiments, the compositions described herein (SAE 5W-30 viscositygrade) exhibit an FEI 2 after 100 hours of aging (%) of about 0.9 toabout 3, such as about 1 to about 2.5, about 1.2 to about 2.2, or evenabout 5 to about 2.

In certain embodiments, the compositions described herein meet or exceedthe standards set forth in the USDA's BioPreferred Program for motoroils, which is currently set at a minimum of 25% bio-based content, asdetermined using ASTM Method D6866. In certain embodiments, thecomposition will exhibit a bio-based content of at least 30%, at least35%, at least 40%, at least 50%, at least 60%, at least 75%, at least85%, or even at least 90%. In certain embodiments, the engine oilcomposition will exhibit a bio-based content of about 25% to about 90%,such as about 25% to about 85%, about 25% to about 75%, about 25% toabout 65%, about 25% to about 50%, about 25% to about 35%, or even about30% to about 45%.

In certain embodiments, one or more of the optional additives discussedherein, such as certain metal deactivator packages, may comprise a fattyacid or fatty acid derivative or precursor, which may increase the acidvalue (e.g., total acid number) of the composition. Without being boundto any particular theory, in certain embodiments, it is believed thatincreasing the acid value of the composition may result in decreasedoxidative stability of the composition, and thus adversely affectingresults of tests conducted according to Sequence IIIG. Accordingly, incertain embodiments, the composition will be substantially free of fattyacid components, such as free fatty acids, and/or have a low acid value.

In certain embodiments is described a method of preparing an estolidecomposition, said method comprising selecting an estolide base oil;reducing the acid value of the estolide base oil to provide a low-acidestolide base oil; and combining the low-acid estolide base oil with atleast one antioxidant. In certain embodiments, reducing the acid valueof the estolide base oil to provide a low-acid estolide base oilcomprises contacting said estolide base oil with at least oneacid-reducing agent. In certain embodiments, the at least oneacid-reducing agent is selected from any suitable agent, such as, forexample, one or more of activated carbon, magnesium silicate (e.g.,Magnesol®), aluminum oxide (e.g., Alumina), silicon dioxide, a zeolite,a basic resin, and an anionic exchange resin. In certain embodiments,the acid value of the at least one estolide base oil is reduced to anyof the levels described herein, such as about 0.1 mg KOH/g or lower. Incertain embodiments, the combination of the low-acid estolide base oiland the at least one antioxidant will have a time value similar to thetimes described herein for other estolide base oils when tested in arotating pressurized vessel oxidation test using ASTM Method 2272-11,such as about 500 minutes, about 600 minutes, about 700 minutes, about800 minutes, about 900 minutes, or even about 1000 minutes or more.

In certain embodiments, the composition comprises, or consistsessentially of, an estolide base oil, a detergent inhibitor, andoptionally an antioxidant. In certain embodiments, the engine oilcomposition further comprises a non-estolide base oil and/or a viscositymodifier. In certain embodiments, the non-estolide base oil comprises atleast one mineral oil or semi-synthetic oil. Accordingly, in certainembodiments, the engine oil composition will exclude synthetic base oilssuch as PAOs and/or non-estolide synthetic esters. In certainembodiments, the engine oil composition will exclude additionaladditives such as pour point depressants and/or polyalkylene glycols.

In certain embodiments, the compositions may be suitable for use as atwo-cycle or four-cycle lubricant. In certain embodiments, thecomposition may be suitable for use as a passenger car motor oil (PCMO),a crankcase oil, a transmission fluid, or a gearbox oil. In certainembodiments, the composition does not comprise a fuel (e.g., internalcombustion fuel such as gasoline or diesel), and is not intended to bemixed into a fuel. Thus, in certain embodiments, the composition doesnot comprise a two-cycle and/or diesel engine lubricant.

As illustrated below, compound 100 represents an unsaturated fatty acidthat may serve as the basis for preparing the estolide compoundsdescribed herein.

In Scheme 1, wherein x is, independently for each occurrence, an integerselected from 0 to 20, y is, independently for each occurrence, aninteger selected from 0 to 20, n is an integer greater than or equal to1, and R₁ is an optionally substituted alkyl that is saturated orunsaturated, and branched or unbranched, unsaturated fatty acid 100 maybe combined with compound 102 and a proton from a proton source to formfree acid estolide 104. In certain embodiments, compound 102 is notincluded, and unsaturated fatty acid 100 may be exposed alone to acidicconditions to form free acid estolide 104, wherein R₁ would represent anunsaturated alkyl group. In certain embodiments, if compound 102 isincluded in the reaction, R₁ may represent one or more optionallysubstituted alkyl residues that are saturated or unsaturated andbranched or unbranched. Any suitable proton source may be implemented tocatalyze the formation of free acid estolide 104, including but notlimited to homogenous acids and/or strong acids like hydrochloric acid,sulfuric acid, perchloric acid, nitric acid, triflic acid, and the like.

Similarly, in Scheme 2, wherein x is, independently for each occurrence,an integer selected from 0 to 20, y is, independently for eachoccurrence, an integer selected from 0 to 20, n is an integer greaterthan or equal to 1, and R₁ and R₂ are each an optionally substitutedalkyl that is saturated or unsaturated, and branched or unbranched, freeacid estolide 104 may be esterified by any suitable procedure known tothose of skilled in the art, such as acid-catalyzed reduction withalcohol 202, to yield esterified estolide 204. Other exemplary methodsmay include other types of Fischer esterification, such as those usingLewis acid catalysts such as BF₃.

In all of the foregoing examples, the compounds described may be usefulalone, as mixtures, or in combination with other compounds,compositions, and/or materials.

Methods for obtaining the novel compounds described herein will beapparent to those of ordinary skill in the art, suitable proceduresbeing described, for example, in the examples below, and in thereferences cited herein.

EXAMPLES Analytics

Nuclear Magnetic Resonance:

NMR spectra were collected using a Bruker Avance 500 spectrometer withan absolute frequency of 500.113 MHz at 300 K using CDCl₃ as thesolvent. Chemical shifts were reported as parts per million fromtetramethylsilane. The formation of a secondary ester link between fattyacids indicating the formation of estolide was verified with 1H NMR by apeak at about 4.84 ppm.

Estolide Number (EN):

The EN was measured by GC analysis.

Iodine Value (IV):

The iodine value is a measure of the total unsaturation of an oil. IV isexpressed in terms of centigrams of iodine absorbed per gram of oilsample. Therefore, the higher the iodine value of an oil the higher thelevel of unsaturation is of that oil. Estimated by GC analysis.

Gas Chromatography (GC):

GC analysis was performed to evaluate the estolide number (EN) andiodine value (IV) of the estolides. This analysis was performed using anAgilent 6890N series gas chromatograph equipped with a flame-ionizationdetector and an autosampler/injector along with an SP-2380 30 m×0.25 mmi.d. column.

The parameters of the analysis were as follows: column flow at 1.0mL/min with a helium head pressure of 14.99 psi; split ratio of 50:1;programmed ramp of 120-135° C. at 20° C./min, 135-265° C. at 7° C./min,hold for 5 min at 265° C.; injector and detector temperatures set at250° C.

Measuring EN and IV by GC:

To perform this analysis, the fatty acid components of an estolidesample were reacted with MeOH to form fatty acid methyl esters by amethod that left behind a hydroxy group at sites where estolide linkswere once present. Standards of fatty acid methyl esters were firstanalyzed to establish elution times.

Sample Preparation:

To prepare the samples, 10 mg of estolide was combined with 0.5 mL of0.5M KOH/MeOH in a vial and heated at 100° C. for 1 hour. This wasfollowed by the addition of 1.5 mL of 1.0 M H₂SO₄/MeOH and heated at100° C. for 15 minutes and then allowed to cool to room temperature.After which time, 1 mL of H₂O and 1 mL of hexane were added to the vialand the resulting liquid phases were mixed thoroughly. The layers werethen allowed to phase separate for 1 minute. The bottom H₂O layer wasremoved and discarded. A small amount of drying agent (Na₂SO₄ anhydrous)was then added to the organic layer after which the organic layer wasthen transferred to a 2 mL crimp cap vial and analyzed.

EN Calculation:

The EN is measured as the percent hydroxy fatty acids divided by thepercent non-hydroxy fatty acids. As an example, a dimer estolide wouldresult in half of the fatty acids containing a hydroxy functional group,with the other half lacking a hydroxyl functional group. Therefore, theEN would be 50% hydroxy fatty acids divided by 50% non-hydroxy fattyacids, resulting in an EN value of 1 that corresponds to the singleestolide link between the capping fatty acid and base fatty acid of thedimer.

IV Calculation:

The iodine value is estimated by the following equation based on ASTMMethod D97 (ASTM International, Conshohocken, Pa.):

${IV} = {\sum{100\frac{A_{f}{MW}_{I}{db}}{{MW}_{f}}}}$

-   -   A_(f)=fraction of fatty compound in the sample    -   MW₁=253.81, atomic weight of two iodine atoms added a double        bond    -   db=number of double bonds on the fatty compound    -   MW_(f)=molecular weight of the fatty compound

The properties of the exemplary estolide base stocks and compositionsare described herein are identified in Tables 1-3.

Other Measurements:

Except as otherwise described, pour point is measured by ASTM MethodD97, cloud point is measured by ASTM Method D2500, viscosity/kinematicviscosity is measured by ASTM Method D445, and viscosity index ismeasured by ASTM Method D2270.

Example 1

The acid catalyst reaction was conducted in a 50 gallon PfaudlerRT-Series glass-lined reactor. Oleic acid (65 Kg, OL 700, Twin Rivers)was added to the reactor with 70% perchloric acid (992.3 mL, AldrichCat#244252) and heated to 60° C. in vacuo (10 torr abs) for 24 hrs whilecontinuously being agitated. After 24 hours the vacuum was released.2-Ethylhexanol (29.97 Kg) was then added to the reactor and the vacuumwas restored. The reaction was allowed to continue under the sameconditions (60° C., 10 torr abs) for 4 more hours. At which time, KOH(645.58 g) was dissolved in 90% ethanol/water (5000 mL, 90% EtOH byvolume) and added to the reactor to quench the acid. The solution wasthen allowed to cool for approximately 30 minutes. The contents of thereactor were then pumped through a 1μ filter into an accumulator tofilter out the salts. Water was then added to the accumulator to washthe oil. The two liquid phases were thoroughly mixed together forapproximately 1 hour. The solution was then allowed to phase separatefor approximately 30 minutes. The water layer was drained and disposedof. The organic layer was again pumped through a 1μ filter back into thereactor. The reactor was heated to 60° C. in vacuo (10 torr abs) untilall ethanol and water ceased to distill from solution. The reactor wasthen heated to 100° C. in vacuo (10 torr abs) and that temperature wasmaintained until the 2-ethylhexanol ceased to distill form solution. Theremaining material was then distilled using a Myers 15 CentrifugalDistillation still at 200° C. under an absolute pressure ofapproximately 12 microns (0.012 torr) to remove all monoester materialleaving behind estolides.

Example 2

The acid catalyst reaction was conducted in a 50 gallon PfaudlerRT-Series glass-lined reactor. Oleic acid (50 Kg, OL 700, Twin Rivers)and whole cut coconut fatty acid (18.754 Kg, TRC 110, Twin Rivers) wereadded to the reactor with 70% perchloric acid (1145 mL, AldrichCat#244252) and heated to 60° C. in vacuo (10 torr abs) for 24 hrs whilecontinuously being agitated. After 24 hours the vacuum was released.2-Ethylhexanol (34.58 Kg) was then added to the reactor and the vacuumwas restored. The reaction was allowed to continue under the sameconditions (60° C., 10 torr abs) for 4 more hours. At which time, KOH(744.9 g) was dissolved in 90% ethanol/water (5000 mL, 90% EtOH byvolume) and added to the reactor to quench the acid. The solution wasthen allowed to cool for approximately 30 minutes. The contents of thereactor were then pumped through a 1μ filter into an accumulator tofilter out the salts. Water was then added to the accumulator to washthe oil. The two liquid phases were thoroughly mixed together forapproximately 1 hour. The solution was then allowed to phase separatefor approximately 30 minutes. The water layer was drained and disposedof. The organic layer was again pumped through a 1μ filter back into thereactor. The reactor was heated to 60° C. in vacuo (10 torr abs) untilall ethanol and water ceased to distill from solution. The reactor wasthen heated to 100° C. in vacuo (10 torr abs) and that temperature wasmaintained until the 2-ethylhexanol ceased to distill form solution. Theremaining material was then distilled using a Myers 15 CentrifugalDistillation still at 200° C. under an absolute pressure ofapproximately 12 microns to remove all monoester material leaving behindestolides.

Example 3

The estolides produced in Example 2 were subjected to distillationconditions in a Myers 15 Centrifugal Distillation still at 300° C. underan absolute pressure of approximately 12 microns (0.012 torr). Thisresulted in a primary distillate having a lower EN average (Ex. 3A), anda distillation residue having a higher EN average (Ex. 3B).

Example 4

Estolides were prepared according to the method set forth in Example 2,except the reaction was initially charged with 41.25 Kg of Oleic acidand 27.50 Kg of whole cut coconut fatty acids, to provide an estolideproduct (Ex. 4).

Example 5

Estolides produced according to the method set forth in Example 4 (Ex.4) were subjected to distillation conditions in a Myers 15 CentrifugalDistillation still at 300° C. under an absolute pressure ofapproximately 12 microns (0.012 torr). This resulted in a primarydistillate having a lower viscosity (Ex. 5A), and a distillation residuehaving a higher viscosity (Ex. 5B).

Example 6

Estolides were prepared according to the methods set forth in Examples 4and 5 to provide estolide products of Ex. 4, Ex. 5A, and Ex. 5B, whichwere subsequently subjected to a basic anionic exchange resin wash tolower the estolides' acid value: separately, each of the estolideproducts (1 equiv) were added to a 30 gallon stainless steel reactor(equipped with an impeller) along with 10 wt. % of Amberlite™ IRA-402resin. The mixture was agitated for 4-6 hrs, with the tip speed of theimpeller operating at no faster than about 1200 ft/min. After agitation,the estolide/resin mixture was filtered, and the recovered resin was setaside. Properties of the resulting low-acid estolides are set forthbelow in Table 1, which are labeled Ex. 4*, Ex. 5A*, and Ex. 5B*.

Example 7

Estolides were prepared according to the methods set forth in Examples 4and 5. The resulting Ex. 5A and 5B estolides were subsequentlyhydrogenated via 10 wt. % palladium embedded on carbon at 75° C. for 3hours under a pressurized hydrogen atmosphere to provide hydrogenatedestolide compounds (Ex. 7A and 7B, respectively). The hydrogenated Ex. 7estolides were then subjected to a basic anionic exchange resin washaccording to the method set forth in Example 6 to provide low-acidestolides (Ex. 7A* and 7B*). The properties of the resulting low-acidEx. 7A* and 7B* estolides are set forth below in Table 1.

TABLE 1 Cloud Pour Point Point Viscosity Viscosity Viscosity ° C. ° C.40° C. 100° C. Index Estolide (ASTM (ASTM (ASTM (ASTM (ASTM Iodine BaseStock EN D97) D2500) D445) D445) D2270) Value Ex. 2 1.82 −33 −32 65.411.3 167 13.2 Ex. 1 2.34 −40 −33 91.2 14.8 170 22.4 Ex. 3A 1.31 −30 −3032.5 6.8 175 13.8 Ex. 3B 3.22 −36 −36 137.3 19.9 167 9.0 Ex. 4* 1.86 −29−36 52.3 9.6 170 12 Ex. 5A* 1.31 −27 −30 35.3 7.2 172 13 Ex. 5B* 2.94−33 −36 137.3 19.9 167 7 Ex. 7A* 1.31 −18 −15 35.3 7.2 173 <5 Ex. 7B*2.94 −27 −24 142.7 20.9 171 <5

Example 8

Various compositions were formulated and tested according to SequenceIIIG conditions for compliance ILSAC GF-5 standards. The formulations1-9 are set forth in Table 2. Certain Sequence IIIG performance resultsof formulations 7-9, as compared to certain GF-5 standards, are setforth in Table 3.

TABLE 2 Detergent Estolide Base Non-Estolide Viscosity Inhibitor Antiox.Engine Stock Base Stock Modifier Additive Booster Oil Form. (%) (%) (%)PPD (%) (%) (%) 1 Ex. 5A* — SV277 (0.3) P5710 — (86.5) (1) (12.2) 2 Ex.5A* PAO4 SV277 (0.3) P5710 — (74.5) (10) (3) (12.2) 3 Ex. 5A* PAO4 SV277(0.3) P5710 — (64.5) (20) (3) (12.2) 4 Ex. 5A* Group III SV277 (0.3)P5710 — (74.5) (10) (3) (12.2) 5 Ex. 5A* Group III SV277 (0.3) P5710 —(64.5) (20) (3) (12.2) 6 Ex. 5A* Group II SV277 (0.3) P5710 — (64.5)(20) (3) (12.2) 7 Ex. 5A* PAO4 SV277 (0.3) P5710 — (64) (20) (3.5)(12.2) 8 Ex. 5A* PAO4 SV277 (0.3) P5710 Aminic (60) (23.092) (3.5)(12.158) antiox. (0.95) 9 Ex. 7A* Yubase 4 SV277 — P5710 Aminic (35)(22.95) (3.5) (12.2) antiox. Yubase 6 (1.15) (25.20)

TABLE 3 IIIG Merits GF-5 Limits 7 8 9 ACLWFNL Wear 60 max. 68.3 61.612.1 Rating (μm) PVISFNL Viscosity 150 max. 436.2 230.9 56.5 Increase (%@ 40° C.) Weighted Piston 4 min. 7.21 8.44 8.46 Deposit (merits) HotStuck Rings None 1 None None IIIGB - Phos. 79% min. 94 92.5 85.7Retention IIIGA - Used <60,000 cP 197,000 cP 58,000 cP 24,000 cP Oil MRV@ −30° C. @ −30° C. @ −30° C. @ −30° C. IIIGA - Used <7,000 cP — — 6,180cP Oil CCS @ −25° C. @ −25° C. Bio-Content (USDA 25% min. 52.5% 49.2%28.7% Biopreferred Program) Result — Fail Fail Pass

Example 9

Formulation 9 (as set forth in Table 2) was tested according to SequenceIVA and Sequence VIII conditions for compliance ILSAC GF-5 standards.The results of those tests, as compared to certain GF-5 standards, areset forth in Tables 4 and 5.

TABLE 4 IVA Merits GF-5 Limits Formulation 9 Average cam wear, 7position 90 max. 1.06 average (μm) Result — Pass

TABLE 5 VIII Merits GF-5 Limits Formulation 9 Bearing weight loss (mg)26 max. 20.5 10-hr stripped KV @ 100° C. 9.3 min. 9.52 (cSt) Result —Pass

Example 10

Estolides were prepared according to the method set forth in Example 2,except the initial charging of oleic acid and whole cut coconut fattyacids was altered to provide two different estolide compositions havingviscosities in the range of about 6 cSt to about 7 cSt. The resultingestolide products were subjected to distillation conditions in a Myers15 Centrifugal Distillation still at 300° C. under an absolute pressureof approximately 12 microns (0.012 torr). This resulted in two separateprimary distillates having a lower viscosities (Ex. 10A, 10B), and adistillation residues having higher viscosities (Ex. 10C, 10D). The Ex.10A and 10B estolides were subsequently hydrogenated via 10 wt. %palladium embedded on carbon at 75° C. for 3 hours under a pressurizedhydrogen atmosphere to provide hydrogenated estolide compounds. Thehydrogenated Ex. 10A and 10B estolides were then subjected to a basicanionic exchange resin wash according to the method set forth in Example6 to provide low-acid estolides (Ex. 10A* and 10B*). The properties ofthe resulting low-acid Ex. 10A* estolides included a kinematic viscosityof 6.8 cSt @ 100° C. and an EN of less than 1.5, while the low-acid Ex10B* estolides exhibited properties that included a kinematic viscosityof 6.3 cSt @ 100° C. and an EN of less than 1.5.

Example 11

The composition of formulation 9 was prepared as set forth in Table 2,except the Ex. 7A* estolides were replaced with Ex. 10A* estolide andEx. 10B* estolides (formulations 11A and 11B, respectively). Theresulting formulations were tested according to Sequence VID conditions(ASTM D7589) for compliance with ILSAC GF-5 resource conservingstandards. The results of those tests, as compared to GF-5 standards,are set forth in Table 6.

TABLE 6 VID Merits GF-5 Test #1 Test #2 Test #3 Test #4 Test #5 (FEIXW-30 viscosity grade) Limits (11A) (11A) (11A) (11A) (11B) FEI sumafter 60 hrs aging 1.9% min. 1.20% 1.40% 1.77% 1.47% 3.30% FEI sum after100 hrs aging 0.9% min. 0.36% 0.29% 0.52% 0.57% 1.73% Result — Fail FailFail Fail Pass

1. A composition comprising: an additive package; and an estolide baseoil comprising at least one estolide compound. 2-117. (canceled)